TW201042094A

TW201042094A - Apparatus and methods for chemical electrodeposition on a substrate for solar cell fabrication

Info

Publication number: TW201042094A
Application number: TW099111551A
Authority: TW
Inventors: Kurt H Weiner; Gaurav Verma; Doron Gal
Original assignee: Reel Solar Inc
Priority date: 2009-04-14
Filing date: 2010-04-13
Publication date: 2010-12-01
Also published as: US20100258444A1; WO2010120702A1

Abstract

The invention relates generally to electrodeposition apparatus and methods. The invention finds particular use in fabricating thin film solar cells. Electrodeposition is improved by using a continuous thin film flow of electrodeposition solution between a substrate and a counter electrode, positioned in close proximity to each other, while the plating current is applied. Apparatus for carrying out methods described herein are highlighted particularly by flow manifolds that allow electrodeposition in the manner described.

Description

201042094 · 六、發明說明：【發明所屬之技術領域】本發明一般而言係關於電沉積裝置及方法。特定而言，本發明之方法及裝置用於太陽能電池製造。相關申請案交又參考 •本申請案根據35 U.SX. § 119主張序㈣為6i/i69,2ii 之美國臨時申請案及序列號為61/1?1，，之美國臨時申請帛之優先權之利益’出於各種目的該兩個申請案以引用方 Ο 式併入本文中。【先前技術】電沉積係-電鍍製程，其使用電流以自—溶液還原或氧化-所期望材料之化學物質且用一薄層彼材料來塗佈一導電基板。一電鑛裝置通常包含兩個電極：充當一個電極之 -基板及-反電極。另外，亦可採用—參考電極。在一電沉積製程中，通常，欲塗佈之部分係該等電極中之一者且〇㈣材料係供應自該等電極浸沒於其中之電解液。在電鍵時’給該電解液週期性地補充正被沉積於該基板上之化學物質。有時，未被塗佈之電極可係該等化學物質之一來源以便補充該電解溶液。太陽月b或光伏打電池係藉由光伏打效應將光子轉換成電 ’ U件。將太陽能電池組裝在m作太陽能面板、太陽月匕模組或光伏打陣列。太陽能電池係堆疊結構，其具有堆邊於用於支樓該堆疊之一基板上。存在諸多用於製造該堆疊之個別層之製造技術。一種特別有用之方法係電沉 147727.doc 201042094 積，然而，習用裝置及方法在此方面存在缺點。因此’需要用於電沉積之經改良裝置及方法。倘若需要可再生能源，則經改良裝置及方法對於太陽能電池製造特別重要。【發明内容】本發明一般而言係關於電沉積裝置及方法。特定而令，本發明用於製造薄膜太陽能電池。發明者已發現可藉由在施加電鍍電流之同時於一基板與一反電極之間使用電沉積溶液之一大致連續流（舉例而言，層流或紊流）來以諸多方式改良電沉積’其中S亥基板與該反電極經定位而彼此極接近’舉例而言’約為幾毫米或更小。特定而言，用於實施本發明之方法之裝置的著重點在於允許以所述之方式進行電沉積之新穎流動歧管。一個實施例係一種用於製造一光伏打電池之電沉積裝置’其包含：（i) 一移動總成，其用於在電沉積期間極接近 (舉例而言，約為幾毫米或更小）於一反電極而定位一基板；及（ii) 一流動歧管，其經組態以使一電解液在該基板與一反電極之間流動且連續地在該基板之電鍍表面與該反電極之間供應電解液；其中該反電極定位於該流動歧管上或係該流動歧管之一組成組件。特定而言，本文中所述之裝置用於採用係一連續片型基板之一基板以便實現薄膜之經改良大量生產時。下文更詳細地闡述數個流動歧管實施例。另一實施例係一種電沉積方法，其包含：在一基板之 147727.doc 201042094 電鍍表面極接近（舉例而言，約為幾毫米或更小）於一反電極之同時使用向該I板供應一電解液之一大致連續供應之一流動歧管來使電解液在該基板與該反電極之間流動；及 . (11)在該基板與該反電極之間施加一電鍍電位；其中該反 • 紙經組態以大致跨過該基板之至少一個維度且定位於該流動歧管上或係該流動歧管之一組成組件。下文聞述本發明之方法之特定態樣。【實施方式】 Ο A.製作一太陽能電池圖1繪不典型薄膜太陽能電池1 00之一經簡化圖解性剖視圖。如所圖解說明，薄膜太陽能電池通常包含以下組件.囊封物105、基板J J 〇、一背部接觸層u 5、一吸收器層120、-冑口層125、一頂部接觸層13〇及頂部囊封物層13 5。背部囊封物通常可用以提供用於電池之囊封且提供機械〇纟撐。背部囊封物可由提供充分密封、防潮、足夠機械支摔、易於製造、處置及諸如此類之諸多不同材料製= 诸多薄膜太陽能電池實施方案中，f部囊封物由玻璃形成’但可使用其他適合材料。土板曰亦可用以提供針對太陽能電池之製造之機械支擇。該基板亦可提供電連接性。在諸多薄膜太陽能電池中，該基板及背部囊封物相同。在此等實例中，通常使用玻璃板。當亦期望電連接性時，可使用塗佈有一透明導電塗層之玻璃。 147727.doc 201042094 一背部接觸層可由提供至太陽能電池之接觸中之—者之材料之-薄膜形成。通常，用於該背部接觸層之材料經挑選以使得最小化關於自/向該吸收器層流動之電子/電洞之接觸電阻。可藉由製造一歐姆或一穿随背部接觸層來達成此結果。此背部接觸層可由諸多不同材料形成此取決於薄膜太陽能電池之類型。舉例而言，在銅銦鎵二砸化物 (CIGS)太陽能電池中，此層可仙。在碲化鑛⑽叫薄膜太陽能電池中，舉例而言，此背部接觸層可由錦或鋼製成。此等材料可僅係說明性實例。亦即，該背部接觸層之材料組成取決於電池中所用之吸收器材料之類型。一背部接觸層臈之厚度通常在幾微米之範圍内。該吸收器層係通常吸收人射光子（圖i中由波紋形箭頭線指示）且將其等轉換為電子之一薄膜材料。此吸收器材料通常係半導電且可係一 P型或一 η型半導體。舉例而言，一吸收器層可由CIGS、CdTe或非晶吩形成。該吸收器層之厚度取決於該半導電材料且通常约為若干微米（自幾微米至數十微米不等）。 -窗口層亦通常係半導電材料之一薄膜，其產生與該吸收器層之-”接合面且另外允許在所關注之能量狀態 (energy regime)下之最大數目之光子穿過而到達該吸收器層。該窗口層可係一 η型或p型半導體，此取決於用於該吸收器層之材料。舉例而言，對於CdTe&CIGS薄膜太陽能電池，該f 口層可由硫化鎘（CdS)n型半導體形成。此層之典型厚度約為幾微米。 147727.doc 201042094 一頂部接觸ϋ常係提供至太陽能電池之接觸中之一者之材料之/專冑。該頂部接觸由對太陽能電;也之所關注能量狀態下之光子係透明之一材料製成。此頂部接觸層通常係 . 透明導電氧化物（TCO)。對於CdTe、CIGS及非晶矽薄膜太陽敗•電池，舉例而言，該頂部接觸可由氧化銦錫（ιτ〇) 或經摻雜氧化鋅（Ζη〇)形成。該頂部接觸層厚度可約為數十微米。 ◎ 頂部囊封物層可用以為電池提供環境保護及機械支 #。该頂部囊封物由在所關注之光子能量狀態下係高度透月之材料形成。舉例而言，此頂部囊封物層可由玻璃形成。通常端視終端使用者之需要而將薄膜太陽能電池串列、 f列或以此兩種方式連接以製造一太陽能模組或面板。該等太陽肖b電池經連接以達成該面板之所期望電壓及電流特 f生連接在一起以製造該面板之電池之數目取決於該等電〇、池之開路電壓、短路電流且取決於該面板之所期望電壓及電流輸出。舉例而言，可藉由在電池製造之製程期間進行雷射切割以用於隔離及/或互連來實施該互連方案。一旦製成此等面板，即將諸如雙通二極體、整流器、連接器、電纜、支撐結構等額外組件附接至該等面板以在現場對其進行安裝以產生t。舉例而言，安裝可係在家庭、大型商業建築物设施、大利用規模太陽能發電農場中及太空中 (舉例而言，用以給衛星及宇宙飛船供電）。如上文所提及，電沉積係用於沉積薄臈太陽能電池之各 H7727.doc 201042094 種層之一有吸引力的方法。已開發用於使用電沉積來沉積背部接觸、吸收器、窗口及頂部接觸層之製程。照慣例’舉例而言，以自一頂部囊封物層、一頂部接觸層、一窗口層、一吸收器層、一背部接觸層等開始之一次序（亦即，以與參考圖！闡述該等層相反之一次序）構造太陽能電、池光伏打堆疊。圖2顯示習用光伏打堆疊形成之一圖解性圖解說明。出於圖解s兑明目的’根據基於CdTe之太陽能電池閣述圖2。該製程以頂部囊封物層開始，且藉由隨後沉積頂部接觸層、窗口層、吸收器層等來建立該電池堆疊。製造次序由圖2中之粗箭頭指示。除所述層以外還可形成其他層且所述層中之某些層之形成係可選，此取決於所期望電池堆疊結構。再次參考圖2，可首先將TC〇塗佈之玻璃（舉例而言，頂部囊封物層205及頂部接觸層2〗〇)清潔、烘乾、切割至適當大小且對邊緣進行接縫處理。具有透明導電氧化物塗層 (舉例而言，氧化銦錫、經氟化氧化錫及經摻雜氧化辞）之浮法玻璃商業上可自各種供應商購得，舉例而言， Pilkington of Toledo，〇hi〇在商標 TEC GlassTM 下及 ppG Industries of Pittsburgh, Pennsylvania^ SUNGATE™ 3〇〇^ SUNGATE™ 500下出售之玻璃。TEC⑴咖顶係塗佈有一經氟化氧化錫導電層之一玻璃。各種溶劑（舉例而言，去離子水、醇類、洗蘇劑及諸如此類）可用於清潔該破璃。亦存在適於清潔大基板之諸多商業上可購得之工業級破璃 147727.doc 201042094 清洗裝置，舉例而言，Lisec™ (可自（LISEC Maschinenbau Gmbh of Seitenstetten，Austria)購得之一玻璃清洗裝置及製程之一商品名稱）。一旦清潔IT0塗佈之玻璃，然後即可藉由使用（舉例而言）鎘鹽與元素硫組合物之一水溶液來沉積一 CdS層215。該溶液不必係水性的。亦即，可使用諸如二甲亞砜 (DMSO)等其他溶劑。可使用電沉積來進行此沉積。對於電沉積，ITO塗佈之玻璃可形成該等電極中之一者。舉例而言，另一電極可由石墨製成，且舉例而言，該電解液可係鎘鹽與元素硫之一 DMS0溶液。在該等電極之間施加電位以便將CdS自該溶液沉積至ITO塗佈之玻璃基板上。沉積該C d S層之另一方法係化學沉積，舉例而言，經由濕化學或乾式應用（諸如，CVD)。所沉積之CdS係一 η型半導體且其厚度通常係在500 Α與1 μηι之間。在該沉積之後，接著可（舉例而言）在一惰性氣氛（諸如，氬）下將該層退火以達成膜緻密化及顆粒生長，以改良該CdS膜之電與機械性質。然後，舉例而言，可自含有鎘鹽及氧化碲之一酸性或鹼性介質以電化學方式將碲化鎘層220沉積於該CdS/TCO/玻璃堆疊（現係用於電沉積之一基板）上。在此製程中，該 CdS/TCO/玻璃基板形成該等電極中之一者且鉑或其他材料可用作另一電極。舉例而言，，該電解液可含有存於諸如水、DMSO或其他溶劑等溶劑中之酸性或鹼性介質以及鎘鹽及氧化碲。通常沉積厚度範圍係自1 μιη至10 μπι之膜。 147727.doc 201042094 然後，可在一空氣或氧耽或CdCl2環境中在大約5〇〇。〇下將蹄化錫膜退火以便改良該膜之電性質且亦將該CdTe膜轉換為一 P型半㈣。據信，此等方法最佳化顆粒大小且因此改良該等膜之電性質。在此CdTe沉積及退火之後，通常執行一雷射切割製程以自特定區（未顯示）移除CdS及CdTe。在此切割作業中，利用該雷射切割以便自太陽能面板之特定區燒蝕cds及201042094 · VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to an electrodeposition apparatus and method. In particular, the method and apparatus of the present invention are used in solar cell fabrication. The relevant application is also referred to. • This application is based on 35 U.SX. § 119. The preamble (4) is the US provisional application of 6i/i69, 2ii and the serial number is 61/1?1. Benefits of the Rights 'The two applications are hereby incorporated by reference for all purposes. [Prior Art] Electrodeposition-electroplating process using a current to reduce or oxidize a chemical from a desired material and coating a conductive substrate with a thin layer of material. An electro-mineral device typically comprises two electrodes: a substrate that serves as an electrode and a counter electrode. Alternatively, a reference electrode can be used. In an electrodeposition process, typically, the portion to be coated is one of the electrodes and the 〇 (4) material is supplied from the electrolyte in which the electrodes are immersed. The electrolyte is periodically replenished with the chemical being deposited on the substrate at the time of the key. Sometimes, the uncoated electrode may be sourced from one of the chemicals to supplement the electrolytic solution. The solar moon b or photovoltaic cell converts photons into electricity U-pieces by the photovoltaic effect. The solar cells are assembled in a solar panel, a solar moon module or a photovoltaic array. A solar cell stack structure having a stack on a substrate for the stack of the stack. There are many manufacturing techniques for fabricating the individual layers of the stack. A particularly useful method is the electrical sink 147727.doc 201042094, however, conventional devices and methods have disadvantages in this regard. Therefore, there is a need for improved apparatus and methods for electrodeposition. Improved devices and methods are particularly important for solar cell manufacturing if renewable energy is required. SUMMARY OF THE INVENTION The present invention generally relates to electrodeposition apparatus and methods. Specifically, the present invention is used to manufacture a thin film solar cell. The inventors have discovered that electrodeposition can be improved in a number of ways by using a substantially continuous flow (e.g., laminar or turbulent flow) between a substrate and a counter electrode while applying a plating current. Wherein the S-substrate and the counter-electrode are positioned in close proximity to each other 'for example' about a few millimeters or less. In particular, the apparatus for carrying out the method of the present invention focuses on a novel flow manifold that allows for electrodeposition in the manner described. One embodiment is an electrodeposition apparatus for fabricating a photovoltaic cell comprising: (i) a mobile assembly for very close proximity during electrodeposition (for example, on the order of a few millimeters or less) Positioning a substrate on a counter electrode; and (ii) a flow manifold configured to flow an electrolyte between the substrate and a counter electrode and continuously on the plated surface of the substrate and the counter electrode An electrolyte is supplied therebetween; wherein the counter electrode is positioned on or is a component of the flow manifold. In particular, the apparatus described herein is used to employ a substrate that is a continuous sheet substrate in order to achieve improved mass production of the film. Several flow manifold embodiments are set forth in more detail below. Another embodiment is an electrodeposition method comprising: supplying 147727.doc 201042094 on a substrate with a plating surface in close proximity (for example, about several millimeters or less) to a counter electrode for supplying the I plate One of the electrolytes supplies a flow manifold substantially continuously to flow the electrolyte between the substrate and the counter electrode; and (11) applying a plating potential between the substrate and the counter electrode; wherein the counter • The paper is configured to span substantially at least one dimension of the substrate and is positioned on or associated with one of the flow manifolds. The specific aspects of the method of the present invention are described below. [Embodiment] Ο A. Making a solar cell Fig. 1 depicts a simplified schematic cross-sectional view of one of the atypical thin film solar cells 100. As illustrated, thin film solar cells typically comprise the following components: encapsulant 105, substrate JJ, a back contact layer u 5, an absorber layer 120, a mouthwash layer 125, a top contact layer 13 and a top pocket. Sealing layer 13 5. Back packs are typically used to provide encapsulation for the battery and to provide mechanical 纟 support. The back pack can be made from a variety of materials that provide adequate sealing, moisture resistance, adequate mechanical support, ease of manufacture, disposal, and the like. In many thin film solar cell embodiments, the f-encapsulation is formed of glass 'but other suitable material. Earthboard can also be used to provide mechanical support for the manufacture of solar cells. The substrate can also provide electrical connectivity. In many thin film solar cells, the substrate and the back encapsulant are the same. In these examples, glass plates are typically used. When electrical connectivity is also desired, a glass coated with a transparent conductive coating can be used. 147727.doc 201042094 A back contact layer can be formed from a film-material that provides the contact to the solar cell. Typically, the material for the back contact layer is selected such that the contact resistance with respect to the electrons/holes flowing from/to the absorber layer is minimized. This can be achieved by making one ohm or one wearing the back contact layer. This back contact layer can be formed from a number of different materials depending on the type of thin film solar cell. For example, in a copper indium gallium dichloride (CIGS) solar cell, this layer can be used. In the bismuth ore (10), which is called a thin film solar cell, for example, the back contact layer may be made of brocade or steel. These materials may be merely illustrative examples. That is, the material composition of the back contact layer depends on the type of absorber material used in the battery. The thickness of a back contact layer is typically in the range of a few microns. The absorber layer typically absorbs human photons (indicated by the corrugated arrow lines in Figure i) and converts them into one of the electron film materials. The absorber material is typically semiconducting and can be a P-type or an n-type semiconductor. For example, an absorber layer can be formed from CIGS, CdTe, or amorphous phenothes. The thickness of the absorber layer depends on the semiconducting material and is typically on the order of a few microns (ranging from a few microns to tens of microns). The window layer is also typically a film of semi-conductive material that creates a "junction" with the absorber layer and additionally allows the maximum number of photons under the energy regime to pass through to reach the absorption The window layer can be an n-type or p-type semiconductor depending on the material used for the absorber layer. For example, for a CdTe & CIGS thin film solar cell, the f-layer can be cadmium sulfide (CdS). An n-type semiconductor is formed. The typical thickness of this layer is about a few microns. 147727.doc 201042094 A top contact ϋ is often provided to the material of the solar cell contact. The top contact is made by solar energy; It is also made of a material that is focused on the photon system in the energy state. This top contact layer is usually a transparent conductive oxide (TCO). For CdTe, CIGS, and amorphous germanium films, for example, The top contact may be formed of indium tin oxide (ITO) or doped zinc oxide (Ζη〇). The top contact layer may have a thickness of about several tens of microns. ◎ The top encapsulant layer may be used to provide an environment for the battery. Protective and mechanical support. The top encapsulate is formed from a material that is highly permeable to the moon in the photon energy state of interest. For example, the top encapsulant layer may be formed of glass. The thin film solar cells are connected in series, f, or in two ways to fabricate a solar module or panel. The solar cells are connected to achieve the desired voltage and current of the panel. The number of cells used to fabricate the panel depends on the voltage of the electrodes, the open circuit voltage of the cell, the short circuit current, and the desired voltage and current output of the panel. For example, lasers can be performed during the manufacturing process of the battery. Cutting is used for isolation and/or interconnection to implement the interconnection scheme. Once such panels are made, additional components such as two-pass diodes, rectifiers, connectors, cables, support structures, etc. are attached to the panels To install it on site to generate t. For example, installation can be tied to homes, large commercial building facilities, large-scale solar farms, and space. (For example, to power satellites and spacecraft.) As mentioned above, electrodeposition is an attractive method for depositing various layers of H7727.doc 201042094 for thin tantalum solar cells. The process of depositing back contacts, absorbers, windows, and top contact layers using electrodeposition. As is conventional, for example, from a top encapsulant layer, a top contact layer, a window layer, an absorber layer, A back contact layer, etc., begins with an order (ie, in the order of the opposite of the reference figure!). The solar photovoltaic, pool photovoltaic stacking is constructed. Figure 2 shows a schematic illustration of a conventional photovoltaic stacking. For the purposes of the illustrations, 'based on CdTe-based solar cells, Figure 2. The process begins with a top encapsulant layer and the cell stack is created by subsequent deposition of a top contact layer, a window layer, an absorber layer, and the like. The manufacturing order is indicated by the thick arrows in Figure 2. Other layers may be formed in addition to the layers and the formation of some of the layers may be optional, depending on the desired cell stack structure. Referring again to Figure 2, the TC(R) coated glass (e.g., top encapsulant layer 205 and top contact layer 2) can be first cleaned, dried, cut to the appropriate size and seamed to the edges. Float glass having a transparent conductive oxide coating (for example, indium tin oxide, fluorinated tin oxide, and doped oxidized) is commercially available from various suppliers, for example, Pilkington of Toledo, 〇hi〇 is sold under the trademark TEC GlassTM and under ppG Industries of Pittsburgh, Pennsylvania^ SUNGATETM 3〇〇^ SUNGATETM 500. The TEC (1) coffee top is coated with a glass of a fluorinated tin oxide conductive layer. Various solvents (for example, deionized water, alcohols, sacrificial agents, and the like) can be used to clean the broken glass. There are also many commercially available industrial grade 147727.doc 201042094 cleaning devices suitable for cleaning large substrates, for example, LisecTM (a glass cleaning available from LISEC Maschinenbau Gmbh of Seitenstetten, Austria) One of the equipment and process names). Once the IT0 coated glass is cleaned, a CdS layer 215 can then be deposited by using, for example, an aqueous solution of one of the cadmium salt and elemental sulfur compositions. The solution need not be aqueous. That is, other solvents such as dimethyl sulfoxide (DMSO) can be used. Electrodeposition can be used to perform this deposition. For electrodeposition, ITO coated glass can form one of the electrodes. For example, the other electrode may be made of graphite, and for example, the electrolyte may be a solution of cadmium salt and one of elemental sulfur, DMS0. An electrical potential is applied between the electrodes to deposit CdS from the solution onto the ITO coated glass substrate. Another method of depositing the Cd S layer is chemical deposition, for example, via wet chemical or dry applications such as CVD. The deposited CdS is an n-type semiconductor and its thickness is usually between 500 Å and 1 μm. After the deposition, the layer can then be annealed, for example, under an inert atmosphere such as argon to achieve film densification and particle growth to improve the electrical and mechanical properties of the CdS film. Then, for example, a cadmium telluride layer 220 can be electrochemically deposited from the CdS/TCO/glass stack from an acidic or basic medium containing cadmium salts and cerium oxide (currently used for one substrate of electrodeposition) )on. In this process, the CdS/TCO/glass substrate forms one of the electrodes and platinum or other material can be used as the other electrode. For example, the electrolyte may contain an acidic or basic medium and a cadmium salt and cerium oxide in a solvent such as water, DMSO or other solvent. Films having a thickness ranging from 1 μm to 10 μm are usually deposited. 147727.doc 201042094 Then, it can be at about 5 Torr in an air or oxime or CdCl 2 environment. The shoe tin film is annealed to improve the electrical properties of the film and also convert the CdTe film into a P-type half (four). It is believed that these methods optimize particle size and thus improve the electrical properties of the films. After this CdTe deposition and annealing, a laser cutting process is typically performed to remove CdS and CdTe from a particular zone (not shown). In this cutting operation, the laser cutting is used to ablate cds from specific regions of the solar panel and

CdTe。然而，並非藉由該雷射切割移除導電氧化物(例如，A1摻雜之ZnO或ITO)。然後，可使用（舉例而言）濺鍍或電沉積來將一背部接觸層225沉積於該CdTe層上。舉例而言，可將銅、鎳及/或其他金屬、合金及複合物用於該背部接觸層。此背部接觸製造步驟可後跟（舉例而言）在約150。與約2〇〇。〇之間的溫度下之一退火以形成一歐姆接觸。該背部接觸層可覆蓋該cdTe 層且亦藉由雷射切割製程來填充產生於以以坨狀層中之通孔（未顯示）。在背部接觸層沉積及退火之後，通常可使用雷射切割來自特定區域移除背部接觸層材料，但在此製程中並非触刻掉該CdTe層。此移除步驟可完成用於隔離且在太陽能面板/ 模組中將該等太陽能電池串聯互連之製程。在沉積該背部接觸層之後，可（舉例而言）使用乙稀-乙酸乙婦脂（EVA)來施加-囊封物層23〇。t封物保護光伏打堆疊。可添加玻璃235以用於進一步結構支撐（及保護）該堆疊。 147727.doc -10· 201042094 上述製造製程表示-簡明綱要且此製程之諸多變化形式可用於CdTe薄膜太陽能電池之製造。對於其他類型之薄膜太陽能電池，可採用不同化學品等。在此說明中，出於圖 * 冑說明性目的’已闡述了實例性製程步驟。其他步驟通常冑包含用於互連方案及電池隔離之製造之雷射切割及燒蝕步驟、不同層沉積之間的多個清潔及烘乾步驟及諸如此類之額外細節。所述之層厚度、退火溫度、化學組成等之值僅係說明性的。當針對諸多不同輸出變量最佳化製程時，此等值可在一寬範圍内變化。圖3係如用一連續基板之-習用電沉積裝置300之一經朽化剖面圖解說明。為不使該說明變複雜，裝備之諸如用於控制系統、用於將電位施加至電極之電子裝置、用於電解液之化學處置系統等其他組件未顯示，但通常將包含於該系統中。該系統之不同組件之尺寸可在一大範圍内變化，此取决於針對其設計該裝備之應用。圖3係-連續基板上 ❹之太陽恥電池製造之各種層之習用電沉積中所使用之裝備之一不思圖。如圖所*，裝置3〇〇包含一大池305，其保持電鑛溶㈣〇且_連續基板315穿過該大槽。藉由在該基板 (舉例而5，一金屬箔）與一反電極之間施加一電位來達成-亥基板上之沉積。一大池通常含有電鑛溶液、反電極 ^20及用於將該基板移動經過該電鑛地帶之一機構（舉例而 σ ’輥325)等。該移動荡係沉積發生於其上之基板。此箱亦/成〜電,儿積系統之電極中之一者。該猪電極可由各種材料製成，但通常將係導電、與電解溶液化學相容 147727.doc 201042094 的舉例而5，該治或基板可由銘、錄、鋼及諸如此類製成。該反電極係該系統中之第二電極且通常浸人於該電解溶液中。此反電極可由各種各樣之材料製成。通常，該反電極係導電且與電解溶液化學相容的。舉例而言，該反電極可由諸如鉑及/或石墨等材料形成。採用一連續基板之習用電沉積裝置通常將包含用於將該基板移動經過有效電鑛地帶之__機構。此移動機構可呈輥 3 25之形式。此等輥用以在該反電極上方將該基板移動經過該系統及該電解液以實現電沉積。基板315隨著其在每輥上方通過而捲曲（或彎曲），在此實例中，該箔基板隨著其進出電解槽且到達進一步處理步驟而彎曲四次。若此等輥中之任一者浸入於該電解液中或與其接觸則通常需要注意確保該輥之構造材料係與該電鍍溶液化學相容。該電解液之組成取決於欲沉積之材料。上文相對於圖1 及2闞述了可用於製造該CdTe太陽能電池之不同層之電鍍溶液之實例。習用裝置（諸如，相對於圖3所述之彼裝置）可具有某些顯著缺點。一個缺點係維護，舉例而言，習用電沉積裝備要求該裝備之移動部件浸入於該電鍍溶液中。電鍍溶液可具有可性、腐蝕性化學品，其導致此等部件之降格且產生、’’ S兆戰。此等所浸入部件亦必須使用與此等苛性化學品相谷之材料來製造，此可顯著提高該裝備之成本。習用電沉積裝置之另一缺點與化學品消耗相關。在電沉 H7727.doc -12· 201042094 積裝備之一典型會痛太安+ 4貫施方案中，該化學品消耗可極高。首先，化學品保持於一大槽令，且原位補充該化學品沉Γ質之化學濃度具有挑戰性。其次，以此組態進行之化學沉積亦可發生於該池之壁上及該裝備之所浸入部：上:此非特定或外部沉積增加化學品消耗且亦增加維護之成本及複雜性。再次，為丹人在S用槽型系統中，難以防止應用尹所不期望且佶用讲夕# ^ μ且使用過多電解溶液之在連續基板之兩個 ❹ ❹ 側上之沉積。最後，使用大量潛在有毒化學品亦可 2加安全危險且增加運行該裝備以適當減輕此風險之成 =電沉積裝置之另一缺點與沉積均勾性相關。以此租達成此積均勾性提出顯著挑戰’舉例而言，在習用裝置大致平行板組態困難的。此可產生邊緣效應：導致非均勾沉積。亦難以維持均勾之基板及溶液溫度及均勻之基板電位，從而逸_ 〇Κ Λ 步負面影響沉積均勻性。提供溶液攪拌同時維持—扁平基、係撓性。狹7Γ具有挑戰性，此乃因該箱習用電沉積裳置之又-缺點與模組性及可互換性相關。在該裝備之習㈣施方案巾，針對不同製程㈣相具有挑戰性。為能夠針對不同製程使用該裝備，必須針對母-應料估所浸入部件與不同化學品之材料相容性。不同製程具有不同沉積速率及層厚度要求，此要求用以達成此等結局之變量(舉例而言，電極之長度及/或基板正移動之速率）具有靈活性。到 I47727.doc 13 201042094 對於習用裝置，若該製程由多個沉積組成，則改變運動之速率不易做到。在習用實施方案中，改變電極之長度具有挑戰性，此乃因改變電極之長度將要求改變槽之大小等或因針對製程流程中之最長沉積來設計該槽而顯著未充分利用該槽及化學品。並且，因需要經由一輥系統將該基板導引至一槽中或自該槽中導引出，該基板及其新沉積膜經歷在至少兩個輥上方彎曲（圖3中所繪示之實例中係四個輥）。若使用一個或多個習用電沉積槽及一連續基板來沉積多個層，則形成於該基板上之光伏打堆疊經歷諸多輥上方之多個彎曲，此可負面影響該堆疊之最終效能。 B·裝置及方法僅出於圖解說明目的，本文中有時將電沉積閣述為用於基於CdTe之太陽能電池之製造，但電沉積可用以製造任一數目之其他類型之太陽能電池或其他類型之薄膜產品及/ 或器件。亦即，本發明並不限於此實例性電沉積化學。發明者已發現可使用根據本發明之實施例之方法及裝置來克服（舉例而言）如相對於圖3所述之習用電沉積裝置之缺點中之諸多缺點。更具體而言，且極概括而言，替代將該基板浸入於一電解液體積中，將電解液之—流動施加至該基板之一表面。發明者已發現新穎流動歧管連同經適當組態之適當基板處置及電沉積組件（諸如，電位源控制器及諸如此類）允許在電鍍期間使基板與反電極彼此極接近，此提供優點，舉例而言，使用較少電解液、消除彎曲及將基板導引至一電解槽中之需要、建立實現高度均勻沉積之 147727.doc •14· 201042094 大致平行板條件且消除將移動部件曝露於該槽之需要。下文闡述進一步之優點。下文更詳細地闡述本發明之實施例之各種實施方案。此 . I實施方案意在作為說明性而非限定性實例。―熟習此項技術者將藉由閱讀本文中之說明來瞭解以下實例之其他變 ’ $。將首先Μ述根據本發明之實施例之各種實例性電沉積裝置及方法且其後將闡述此等實施方案之潛在利益。〇施例係-種用於製造-光伏打電…沉積裝置’其包含：⑴-移動總成，其用於在電沉積期間極接近於-反電極i也定位-基板；及（ii)一流動歧管，其經組態以使一電解液在該基板與一反電極之間流動且連續地在該基板之電鍍表面與該反電極之間供應電解液；其中該反電極定位於該流動歧管上或係該流動歧管之一組成組件。在 -個實施例中，該移動總成包含一驅動組件，其經組態以在電沉積期間在大致不彎曲該基板之情形下將該基板移動〇㈣流動歧管及反電極。在—個實施例中，該基板包含一連續片，其包含一導電材料及具有一導電塗層之_材料中之至少-者。舉例而言，導電材料包含紹、不錢鋼、鈦及 . 石墨落。具有一導電塗層之一材料將係（舉例而言）一玻帛、塑膠、聚合物或塗佈有一導電塗層(舉例而言，一導電氧化物，諸如一透明導電氧化物（舉例而言，經敗化之氧化錫、氧化銦錫及諸如此類））之）之其他基板。圖4緣示一流動歧管400之一透視圖，流動歧管_係根據本發明之—個實施方案之一電沉積裝置之-組件。歧管 147727.doc •15- 201042094 4〇0具有一本體405，且在此實例中極410，反雷炻J中具有大致平坦之一反電樣平之-頂部表具有大致與歧管本體405之頂部表面一管之-二二:係根據本發明之實施例之流動歧 ,,,μμ 案’亦即’該反電極可定位於該歧管上，面㈣Τ，整合至或凹進於該流動歧管本體之-表注=Γ::，流動歧f4❹❻具有-電解液入口 (或為矩r 電解液出口倒。雖然在形狀上繪示狀 >祥但入口及出口電解液埠並不限於任一特定幾何形。表，舉例而言’可存在用作與一單個入口及/或出 Z相同之目的之—系列入口及出口。在電沉積期間使一土板（在此實例中’ 一連續片基板425)與反電極·彼此極接近（如由粗雙頭垂直箭頭所指示）。在—個實施例中，該反電極及該基板電鍍表面係大致平行之平面。在一個實施例中，該反電極與該基板在電沉積期間相隔約2_與約^ 賴之間，在另一實施例中，在電沉積期間相隔約2 mm與約軸之間’在又一實施例中，在電沉積期間相隔約； mm與約5 mm之間。在另—實施例中，該反電極與該基板在電》儿積期間相隔約1 mm與約5 mm之間，在另一實施例中，相隔約1 mm與約3 mm之間，在又一實施例中，相隔約1 mm與2 mm之間。在另一實施例中，該反電極與該基板相隔約0.1 mm與約2 mm之間。雖然某些實施例闡述為在基板與反電極之間具有一大致平行平面定向，但在電鍍之前及/或期間該兩個電極可係非平行。舉例而言，類似於半導體技術，在進入至—電解 I47727.doc -16- 201042094CdTe. However, the conductive oxide (e.g., A1-doped ZnO or ITO) is not removed by the laser cutting. A back contact layer 225 can then be deposited on the CdTe layer using, for example, sputtering or electrodeposition. For example, copper, nickel and/or other metals, alloys and composites can be used for the back contact layer. This back contact manufacturing step can be followed by, for example, about 150. With about 2 baht. One of the temperatures between turns is annealed to form an ohmic contact. The back contact layer may cover the cdTe layer and also fill the vias (not shown) created in the germanium layer by a laser cutting process. After the back contact layer is deposited and annealed, laser cutting is typically used to remove the back contact layer material from a particular area, but the CdTe layer is not engraved during this process. This removal step can complete the process for isolating and interconnecting the solar cells in series in a solar panel/module. After depositing the back contact layer, the encapsulation layer 23 can be applied, for example, using ethylene-acetate (EVA). The t seal protects the photovoltaic stack. Glass 235 can be added for further structural support (and protection) of the stack. 147727.doc -10· 201042094 The above manufacturing process represents a concise outline and many variations of this process can be used in the manufacture of CdTe thin film solar cells. For other types of thin film solar cells, different chemicals can be used. In this description, exemplary process steps have been set forth for illustrative purposes. Other steps typically include laser cutting and ablation steps for interconnecting and battery isolation fabrication, multiple cleaning and drying steps between different layer depositions, and the like. The values of the layer thickness, annealing temperature, chemical composition, etc. are merely illustrative. When the process is optimized for many different output variables, the values can vary over a wide range. Figure 3 is an illustration of a decay profile of a conventional electrodeposition apparatus 300, such as a continuous substrate. In order not to complicate the description, other components such as those used in control systems, electronic devices for applying electrical potential to electrodes, chemical treatment systems for electrolytic fluids, and the like are not shown, but will generally be included in the system. The dimensions of the different components of the system can vary over a wide range, depending on the application for which the equipment is designed. Figure 3 is an illustration of the equipment used in the conventional electrodeposition of various layers of the solar shame battery fabricated on a continuous substrate. As shown in the figure *, the device 3A contains a large pool 305 which remains electrically mineralized (tetra) and through which the continuous substrate 315 passes. The deposition on the substrate is achieved by applying a potential between the substrate (e.g., a metal foil) and a counter electrode. A large pool typically contains an electromineral solution, a counter electrode ^20, and a mechanism for moving the substrate through the electromineral zone (for example, σ'roll 325). The mobile layer deposits a substrate on which it is deposited. This box is also / into ~ electric, one of the electrodes of the child system. The pig electrode can be made from a variety of materials, but will typically be electrically conductive and chemically compatible with the electrolytic solution. 147727.doc 201042094 is an example of 5, which can be made from inscriptions, records, steels, and the like. The counter electrode is the second electrode in the system and is typically immersed in the electrolytic solution. This counter electrode can be made of a wide variety of materials. Typically, the counter electrode is electrically conductive and chemically compatible with the electrolytic solution. For example, the counter electrode can be formed of a material such as platinum and/or graphite. A conventional electrodeposition apparatus employing a continuous substrate will typically include a mechanism for moving the substrate through an active ore zone. This moving mechanism can take the form of a roller 35. The rollers are used to move the substrate through the system and the electrolyte over the counter electrode to effect electrodeposition. Substrate 315 is crimped (or bent) as it passes over each roll, in this example, the foil substrate is bent four times as it enters and exits the cell and reaches a further processing step. If either of these rolls is immersed in or in contact with the electrolyte, care must be taken to ensure that the material of the roll is chemically compatible with the plating solution. The composition of the electrolyte depends on the material to be deposited. Examples of electroplating solutions that can be used to make different layers of the CdTe solar cell are described above with respect to Figures 1 and 2. Conventional devices, such as the one described with respect to Figure 3, can have some significant drawbacks. One disadvantage is maintenance. For example, conventional electrodeposition equipment requires that the moving parts of the equipment be immersed in the plating solution. The plating solution can have a corrosive, corrosive chemical that causes such components to degrade and create, ' These immersed parts must also be manufactured using materials that are compatible with such caustic chemicals, which can significantly increase the cost of the equipment. Another disadvantage of conventional electrodeposition devices is related to chemical consumption. In the electric sink H7727.doc -12· 201042094 one of the typical equipment painful Taian + 4 solution, the chemical consumption can be extremely high. First, the chemical remains in a large tank and it is challenging to replenish the chemical in situ. Second, chemical deposition in this configuration can also occur on the wall of the cell and the immersion of the equipment: Top: This non-specific or external deposition increases chemical consumption and also increases the cost and complexity of maintenance. Again, for the Dan people in the S-type slot system, it is difficult to prevent the application of Yin on the two sides of the continuous substrate, which is undesirable and uses too much electrolytic solution. Finally, the use of a large number of potentially toxic chemicals can also increase the safety hazard and increase the operation of the equipment to mitigate this risk. Another disadvantage of the electrodeposition apparatus is related to sedimentation. This renting achieves this product and presents a significant challenge. For example, it is difficult to configure the device in a substantially parallel plate. This produces edge effects: resulting in non-homogeneous deposits. It is also difficult to maintain the temperature of the substrate and the solution and the uniform substrate potential, so that the _ 〇Κ 负面 step negatively affects the deposition uniformity. The solution is stirred while maintaining a flat base and flexibility. Narrowness is challenging because of the drawbacks associated with modularity and interchangeability. In the equipment (4), the scheme towel is challenging for different processes (4). In order to be able to use the equipment for different processes, it is necessary to estimate the material compatibility of the immersed parts with different chemicals for the mother-sink. Different processes have different deposition rates and layer thickness requirements, which are flexible in achieving the variables of these outcomes (for example, the length of the electrodes and/or the rate at which the substrate is moving). To I47727.doc 13 201042094 For conventional devices, if the process consists of multiple deposits, changing the rate of motion is not easy. In conventional embodiments, changing the length of the electrode is challenging, as changing the length of the electrode would require changing the size of the trench, etc. or designing the trench for the longest deposition in the process flow would significantly underutilize the trench and chemistry. Product. Moreover, the substrate and its newly deposited film undergo bending over at least two rolls due to the need to guide the substrate into or out of the slot via a roll system (examples depicted in Figure 3) Medium is four rollers). If one or more conventional electrodeposition baths and a continuous substrate are used to deposit a plurality of layers, the photovoltaic stack formed on the substrate experiences multiple bends above the plurality of rolls, which can negatively impact the final performance of the stack. B. Apparatus and Methods For illustrative purposes only, electrodeposition is sometimes described herein for the fabrication of CdTe-based solar cells, but electrodeposition can be used to fabricate any number of other types of solar cells or other types. Film products and / or devices. That is, the invention is not limited to this exemplary electrodeposition chemistry. The inventors have discovered that methods and apparatus in accordance with embodiments of the present invention can be used to overcome many of the disadvantages of, for example, the conventional electrodeposition apparatus described with respect to Figure 3. More specifically, and in a nutshell, instead of immersing the substrate in an electrolyte volume, a flow of the electrolyte is applied to one of the surfaces of the substrate. The inventors have discovered that novel flow manifolds, along with suitably configured appropriate substrate handling and electrodeposition components, such as potential source controllers and the like, allow the substrate and counter electrode to be in close proximity to each other during electroplating, which provides advantages, for example   use less electrolyte, eliminate bending and the need to guide the substrate into an electrolytic cell, establish a highly uniform deposition 147727.doc •14· 201042094 roughly parallel plate conditions and eliminate the exposure of moving parts to the groove need. Further advantages are explained below. Various embodiments of embodiments of the invention are set forth in more detail below. This .I embodiment is intended to be illustrative and not limiting. —— Those skilled in the art will understand the other variations of the following examples by reading the instructions in this article. Various exemplary electrodeposition apparatus and methods in accordance with embodiments of the present invention will be described first and the potential benefits of such embodiments will be set forth hereinafter.沉积系用于用于光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏光伏沉积光伏沉积沉积沉积沉积a manifold configured to flow an electrolyte between the substrate and a counter electrode and continuously supply an electrolyte between a plating surface of the substrate and the counter electrode; wherein the counter electrode is positioned in the flow One of the components of the flow manifold is formed on the tube. In one embodiment, the mobile assembly includes a drive assembly configured to move the substrate (IV) the flow manifold and the counter electrode during electrodeposition without substantially bending the substrate. In one embodiment, the substrate comprises a continuous sheet comprising at least one of a conductive material and a material having a conductive coating. For example, conductive materials include slag, no steel, titanium, and graphite. A material having a conductive coating will be, for example, a glass, plastic, polymer or coated with a conductive coating (for example, a conductive oxide such as a transparent conductive oxide (for example Other substrates of defeated tin oxide, indium tin oxide, and the like). Figure 4 illustrates a perspective view of a flow manifold 400, which is an assembly of an electrodeposition apparatus according to one embodiment of the present invention. Manifold 147727.doc •15- 201042094 4〇0 has a body 405, and in this example pole 410, the anti-Thunder J has a substantially flat one of the counter-electrical samples - the top table has a substantially manifold body 405 The top surface of the tube-two: according to the embodiment of the present invention, the flow differential,, μμ case 'that is, 'the counter electrode can be positioned on the manifold, face (four) Τ, integrated or recessed in the The flow manifold body - surface note = Γ::, the flow difference f4 ❹❻ has - electrolyte inlet (or the moment r electrolyte outlet. Although the shape is shown > the inlet and outlet electrolyte is not Limited to any particular geometry. Tables, for example, may exist for use as a series of inlets and outlets for the same purpose as a single inlet and/or Z. A soil plate (in this example) during electrodeposition A continuous sheet substrate 425) and the counter electrode are in close proximity to each other (as indicated by the thick double-headed vertical arrows). In one embodiment, the counter electrode and the substrate plating surface are substantially parallel planes. In one embodiment The counter electrode and the substrate are separated by about 2_ during electrodeposition Between the two, in another embodiment, between about 2 mm and about the axis during electrodeposition, in another embodiment, between about 10 mm and about 5 mm during electrodeposition. In another embodiment, the counter electrode and the substrate are separated by between about 1 mm and about 5 mm during the electrical current, and in another embodiment, between about 1 mm and about 3 mm apart. In an embodiment, between about 1 mm and 2 mm apart. In another embodiment, the counter electrode is spaced between the substrate by between about 0.1 mm and about 2 mm. Although certain embodiments are illustrated as being on the substrate and the counter electrode There is a substantially parallel plane orientation between them, but the two electrodes may be non-parallel before and/or during electroplating. For example, similar to semiconductor technology, upon entering - electrolysis I47727.doc -16- 201042094

液中期間及/或在-電鑛製程期間控制一電鍵基板相對於電解液之表面之定向會有幫助。舉例而言，當浸入至該電解液中時…電鐘基板之電鍍下側±可夾帶氣泡。在鑛』間黏附至—基板之表面之氣泡可在所沉積膜中產生孔穴°特別在以—水衫向（亦即，平行於由該電解液之表面所界定之-平面）浸入該基板時，可如此夾帶氣泡。若在法向於該電解液之表面之一軌跡上將該基板纟面弓！入至該電解液中(亦即，該基板在進入該電解液中之前成角度）’則可避免或至少最小化氣泡之夾帶。因此，在一個實施例中’裝置允許成角度地浸入至來自歧管之電解液之一連續流動中。在其他實施例中，在浸入期間或在電沉積期間，可有效地調節基板之定向。有效角度調節係指在定位或電沉積期間在任一時間相對於跨越流動歧管之表面之流動電解液之一理論平面改變基板之角度^此提供各種電沉積情景之靈活性。然而，在一典型但非限定性實例中，採用層流電解液流動（如下文更詳細地闡述），其有助於移除可導致膜缺陷之任何氣泡。再次參考圖4，使基板425與反電極410彼此極接近，且在其等之間建立一電解液流動。由點線箭頭指示此實例中之流動之方向’其首先自入口 415流出且然後退出至出口 420中。在此實例中，可產生（經由未繪示之適當儲液槽及幫浦）一連續流動，其流動至該基板與該反電極之間的空隙中、在該基板與該反電極之間流動且經由出口 420排出。在一個實例中，流動型樣大致係層流。基板425上方 147727.doc -17- 201042094 之點線箭科示該基板㈣於流動歧管彻之移動方向。在個實施例中，在電沉積期間連續移動該連續片基板，在另-實施例中，週期性地重新定位該基板以便在^ 之尚未沉_之—區域上電沉積。在其他實施例/，該電解液流動係紊·流。在某些實施例巾’該基板相對於該流動歧管之該反電極 :續地移動。在-具體實施方案中，該歧管之長度(如圖4 中所繪不之「L」）將取決於該基板正移動之速度、該電沉積製程之沉積速率及欲沉積之材料之厚度。該電極可由以下公式給出：又It is helpful to control the orientation of a key substrate relative to the surface of the electrolyte during the liquid and/or during the electro-mine process. For example, when immersed in the electrolyte, the underside of the plating of the electric clock substrate can be entrained with air bubbles. Bubbles adhering to the surface of the substrate between the minerals can create voids in the deposited film, particularly when immersed in the substrate in a water-shirt orientation (i.e., parallel to the plane defined by the surface of the electrolyte) Can be entrained with air bubbles. If the path is normal to the surface of the electrolyte, the substrate is bowed! Entrainment of the bubbles can be avoided or at least minimized by entering into the electrolyte (i.e., the substrate is angled prior to entering the electrolyte). Thus, in one embodiment the device allows for angular immersion into a continuous flow of electrolyte from the manifold. In other embodiments, the orientation of the substrate can be effectively adjusted during immersion or during electrodeposition. Effective angle adjustment refers to the angle at which the substrate is changed at any one time relative to the theoretical plane of the flowing electrolyte across the surface of the flow manifold during positioning or electrodeposition, thus providing flexibility in various electrodeposition scenarios. However, in a typical but non-limiting example, laminar electrolyte flow (as explained in more detail below) is employed which helps to remove any air bubbles that can cause film defects. Referring again to Figure 4, substrate 425 and counter electrode 410 are brought into close proximity to each other and an electrolyte flow is established between them. The direction of the flow in this example is indicated by a dotted arrow which first flows out of the inlet 415 and then exits into the outlet 420. In this example, a continuous flow (via a suitable reservoir and pump not shown) can be generated that flows into the gap between the substrate and the counter electrode, flowing between the substrate and the counter electrode And discharged through the outlet 420. In one example, the flow pattern is substantially laminar. Above the substrate 425 147727.doc -17- 201042094, the point arrow shows the substrate (4) in the direction of movement of the flow manifold. In one embodiment, the continuous sheet substrate is continuously moved during electrodeposition, and in another embodiment, the substrate is periodically repositioned to be electrodeposited on a region that has not yet been deposited. In other embodiments, the electrolyte flow is turbulent. In some embodiments, the substrate is continuously moved relative to the counter electrode of the flow manifold. In a particular embodiment, the length of the manifold ("L" as depicted in Figure 4) will depend on the speed at which the substrate is moving, the deposition rate of the electrodeposition process, and the thickness of the material to be deposited. The electrode can be given by the following formula:

L = Tx S/R 其中L=電極之長度，τ=欲塗佈之薄之厚度，^沉積之速率且S =基板運動之速度。舉例而言，若欲沉積之層之厚声係！ μ^η，基板正w英尺/分鐘之_速度移動且該層之沉: 速率係1 μηι/分鐘，則該電極之長度將係·_ L=(i英尺 /分鐘）/(1叫/分鐘）=1英尺。在—個實施例中，當在電沉積期間該基板經過該反電極時，該反電極大致跨過該基板之寬度。圖4繪示反電極寬度$「w」。不需使用一單個反電極，而是兩個或更多個適當隔開及/或圖案化之反電極亦可工作’且在本文中闡述「—反電極」之任何地方包含為一替代實施例。圖5 A及5B分別顯示根據本發明之一具體實施方案之用於在一連續基板上電鍍之一電沉積系統500之側剖面及正剖面。 147727.d〇) -18- 201042094 參考圖5A，裝置500具有一流動歧管，其包含具有一電解液入口 515及出口 520之一本體5〇5。由自515至520之虛線則頭指不電解液（如圖5B中所指示之54〇)在電沉積期間之流動。由一輥53〇移動一基板525(舉例而言，一箔），該輥亦可（舉例而言）經由至基板US之背側之一所施加真空來提供溫度控制且保持該基板扁平。由輥53〇上之曲線虛線箭頭指不輥530之移動，其中基板525自基板之一卷或諸如此類遞送至輥530。輥530亦可保護基板525之背側以使得所電沉積之材料僅施加至該基板之一個側。用於移動該基板之一輥係典型的而非必需。在一個實施例中，舉例而 a，由亦可施加電位、提供溫度控制且保持該基板扁平 (如相對於該輥所述）之一滑道結構替換該輥。在該滑道實施例中，在該滑道與該反電極之間將該基板拉動經過該滑道及s亥反電極。在一典型製程中，在基板525與一反電極 5 10之間施加一電位。在此實例中，反電極5丨〇凹進至歧管本體505中以使得該反電極之頂部表面與該歧管本體之頂部表面齊平。該基板在該歧管上方移動，該歧管用以自一個端注入電鍍溶液且自此歧管之另一端抽出此溶液。該基板與第二電極之間的電位差致使來自該電解溶液之一材料 535沉積於基板525之表面上，該表面與在基板525極接近於s亥反電極移動過該反電極時觸碰親530之彼表面相對。在一個實施例中，該基板連續地移動，在另一實施例中，該基板週期性地移動以在該基板未正移動時電沉積。圖5 a 及5B顯示此裝備之一個可能實施方案。雖然顯示一個可能 147727.doc -19- 201042094 實施方案’但其他實施方案亦係可能。舉例而言，可將該裝備反轉以使得該歧管在該移動基板上方，或可垂直或以某一角度定向該等組件以利用重力來（舉例而言）驅動及/或引導電解液流動及/或以慮及其他製造優點。一個或多個電位源在該基板與該電極之間施加一電位差 (舉例而言，經由移動機構）以使得來自該電解溶液之一材料沉積於該基板之一個表面上。該一個或多個電位源可採取任一適合形式，諸如一直流電源（舉例而言一可調節或固定電流源）。在此實施例中，該基板毗鄰於該電極連續地移動以使得來自該溶液之一材料沉積成跨越該基板之整個第一表面之一薄膜。歧管本體505可由諸多不同材料構造，諸如，聚四說乙烤（PTFE ’亦稱為鐵氟龍（Tefl〇n)，其係duP〇nt心L = Tx S/R where L = length of the electrode, τ = thickness of the thin layer to be coated, rate of deposition and S = speed of substrate motion. For example, if you want to deposit a layer of thick sound! μ^η, the substrate moves at a speed of wft/min and the layer sinks: at a rate of 1 μηι/min, the length of the electrode will be _ L = (i ft / min) / (1 call / min ) = 1 foot. In one embodiment, the counter electrode extends substantially across the width of the substrate as it passes through the counter electrode during electrodeposition. Figure 4 shows the counter electrode width $"w". It is not necessary to use a single counter electrode, but two or more suitably spaced and/or patterned counter electrodes may also work 'and wherever the "-counter electrode" is described herein as an alternative embodiment . 5A and 5B respectively show side and front cross-sections of one electrodeposition system 500 for electroplating on a continuous substrate in accordance with an embodiment of the present invention. 147727.d〇) -18- 201042094 Referring to FIG. 5A, the apparatus 500 has a flow manifold including a body 5〇5 having an electrolyte inlet 515 and an outlet 520. The dotted line from 515 to 520 refers to the flow of no electrolyte (54 指示 as indicated in Figure 5B) during electrodeposition. A substrate 525 (e.g., a foil) is moved by a roller 53. The roller can also provide temperature control, for example, via a vacuum applied to one of the back sides of the substrate US and keep the substrate flat. The dashed arrow arrow on the roller 53 refers to the movement of the roller 530, wherein the substrate 525 is delivered to the roller 530 from one of the substrates or the like. Roller 530 can also protect the back side of substrate 525 such that the electrodeposited material is applied only to one side of the substrate. It is typical and not necessary to move one of the rolls of the substrate. In one embodiment, for example, a roller is replaced by a slide structure that also applies a potential, provides temperature control, and maintains the substrate flat (as described with respect to the roller). In the embodiment of the slide, the substrate is pulled between the slide and the counter electrode through the slide and the counter electrode. In a typical process, a potential is applied between substrate 525 and a counter electrode 510. In this example, the counter electrode 5 is recessed into the manifold body 505 such that the top surface of the counter electrode is flush with the top surface of the manifold body. The substrate moves over the manifold for injecting a plating solution from one end and withdrawing the solution from the other end of the manifold. The potential difference between the substrate and the second electrode causes a material 535 from the electrolytic solution to be deposited on the surface of the substrate 525, and the surface touches the parent 530 when the substrate 525 is in close proximity to the counter electrode. The other side is opposite. In one embodiment, the substrate is continuously moved, and in another embodiment, the substrate is periodically moved to electrodeposit while the substrate is not moving. Figures 5a and 5B show one possible implementation of this equipment. Although a possible implementation of 147727.doc -19- 201042094 is shown, other embodiments are possible. For example, the equipment can be reversed such that the manifold is above the moving substrate, or the components can be oriented vertically or at an angle to utilize gravity to, for example, drive and/or direct electrolyte flow. And/or to take into account other manufacturing advantages. One or more potential sources apply a potential difference (e.g., via a moving mechanism) between the substrate and the electrode such that a material from the electrolytic solution is deposited on one surface of the substrate. The one or more potential sources can take any suitable form, such as a DC power source (e.g., an adjustable or fixed current source). In this embodiment, the substrate is continuously moved adjacent to the electrode such that a material from the solution is deposited as a film across one of the entire first surfaces of the substrate. The manifold body 505 can be constructed from a variety of different materials, such as Polytetraethylene (PTFE), also known as Teflon, which is a duP〇nt heart.

Nemours and Company, of Wilmington，Delaware之注冊商標）、全氟烷氧基（PFA)、聚四氟乙烯-全氟甲基乙烯基醚 (MFA)、氟化乙烯丙烯（FEP)、乙烯_四氟乙烯（ETFE)、乙烯-氯三氟乙烯（ECTFE)、聚二氟亞乙烯（PVDF)、四氟乙烯-六氟丙烯-二氟亞乙烯（THV) '聚醚醚酮（PEEKTM係 Victrex 〇f Lancashire, UK之一註冊商標）、聚醚醯亞胺 (PEI)及諸如此類。較佳地，此等材料具有耐化學性、易於機器加工且電絕緣。含氟聚合物通常恰好適合於此等準則。反電極510可由諸多不同材料製成。舉例而言，上文闡述可用於CdTe太陽能電池之不同層之製造之不同電極材料0 147727.doc -20- 201042094 雖然某些實施例闡述反電極與基板之間的關係為反電極大致跨過基板之寬度，但可使用反電極之任何適合尺寸。在一個實施例中’選擇該等尺寸以使得反電極寬於正塗佈之基板，以便可維持一平行板組態且可最小化邊緣電場效應。圖5A圖解說明一反電極寬於在其上方通過之基板。該歧官可視情況包含用於基板之預清潔及沖洗並烘乾之能力。舉例而言，可在該歧管之一個端處添加氮、氬及/Nemours and Company, of Wilmington, registered trademark of Delaware), perfluoroalkoxy (PFA), polytetrafluoroethylene-perfluoromethyl vinyl ether (MFA), fluorinated ethylene propylene (FEP), ethylene _ PTFE Ethylene (ETFE), ethylene-chlorotrifluoroethylene (ECTFE), polydifluoroethylene (PVDF), tetrafluoroethylene-hexafluoropropylene-difluoroethylene (THV) 'polyether ether ketone (PEEKTM system Victrex 〇f Lancashire, one of the UK registered trademarks), polyetherimine (PEI) and the like. Preferably, such materials are chemically resistant, easy to machine, and electrically insulating. Fluoropolymers are usually just right for this criterion. The counter electrode 510 can be made of many different materials. For example, the various electrode materials that can be used in the fabrication of different layers of CdTe solar cells are set forth above. 147727.doc -20- 201042094 although certain embodiments illustrate that the relationship between the counter electrode and the substrate is such that the counter electrode substantially spans the substrate The width, but any suitable size of the counter electrode can be used. In one embodiment, the dimensions are selected such that the counter electrode is wider than the substrate being coated so that a parallel plate configuration can be maintained and the fringe field effect can be minimized. Figure 5A illustrates a counter electrode that is wider than the substrate that passes over it. The ambiguity may include the ability to pre-clean and rinse and dry the substrate. For example, nitrogen, argon, and/or may be added to one end of the manifold.

或空氣簾及/或刀。在一個實施方案中，該或該等氣體將被以管道方式輸入至該歧管中且吹至該基板上以將其烘乾。類似地，對於預清潔及沖洗，可藉由該歧管將去離子水或其他溶劑噴射至該基板上。可在該基板進入電沉積地帶之前及其退出電沉積地帶之後進行預清潔、沖洗及烘乾中之任一者及組合。雖然在本發明之—個實施方案巾，—輥提供用於移動基板/箔之一移動機構，但亦可利用其他移動機構。另外，仁未^地’可將一加熱器附接至移動機構以用於加熱基板。亚^，可提供真空或抽吸至該輥以保持該基板扁平至 :輥上。亦可採用某-其他保持機構以將基板保持於移動 7上。該輥亦可用於施加電位至基板。在—個實施例中’相對於該反電極’此電位可係接地。程要東具有不同組成’此取決於正沉積之層之製柱要衣。上文論述了可用之電解溶液之實例。、冑e场能電池之不同層羯或基板可採取其上欲執行沉積之連續基板之形式且 147727.doc •21· 201042094 二可充當該系統之電極中之一者。可使用不同基板。上文論述了不同類型之電極之實例及對笛之要;^ 該基板亦可採取务求。休取塗佈有一 TCO(其充當電極）形式。在一個蜜竑η上坻喁片之固實施例中，該基板係此一玻璃片施例中，該破璃片係連續實參考圖5Β，基板與反電極51〇之間含有溶液電極之間的間隙之Ή 4 β m 隹”亥兩個該溶液，亦/ 可採用流體表面張力來限制 " 7、P，電解液之一膨脹具有充分流動，極足夠近地靠右—& 邊导電且無f額外密封得流體表面張力用於抑制該溶液、另外，溢流通道545可經構造以容漏出之任何電解液（圖Μ中夫泠、古 ^ Τ未，.’日不&流通道’但—個眘尬 r::::r歧…邊…，或視情心液。若表面張力不足以―:望主:壓力下施加該電解溶可採用密封件。因此，—個實施例係如上所述之進一= 含一個或多個㈣件n該等密封件經組態以引導^ 解液之流動f便在電沉積期間最大化與基板之接觸且最小化產生接觸該基板之連續電解液供應所需之電解液之量。舉例而言，一個或多個密4+ 在封件可用以將電解溶液抑制於電鑛地帶中，且不同機構可用於此抑制。舉例而言，可藉由在該反電極之一個或多袖相丨丨田㈤飞夕個側周圍、在該歧管本體上或極接近於該歧管本體處使用（舉例而言）由相對於歧管51〇所述之 147727.doc •22· 201042094 材料或下文相對於密封元件所述之彼等材料製成之壞來達成充分密封，以幫助流體抑制。在某些實施例中，一個或夕個密封件附接至或極接近於該流動歧管及該反電極中之至夕者。在另一實施例中，該一個或多個密封件係一整體歧管本體之部分。Or air curtains and / or knives. In one embodiment, the or the gases will be piped into the manifold and blown onto the substrate to dry it. Similarly, for pre-cleaning and rinsing, deionized water or other solvent can be sprayed onto the substrate by the manifold. Any one or combination of pre-cleaning, rinsing, and drying can be performed before the substrate enters the electrodeposited zone and exits the electrodeposited zone. Although in the embodiment of the present invention, the roller provides a moving mechanism for moving the substrate/foil, other moving mechanisms can be utilized. Alternatively, a heater can be attached to the moving mechanism for heating the substrate. A vacuum or suction can be provided to the roller to keep the substrate flat to: the roller. A certain other holding mechanism can also be employed to hold the substrate on the movement 7. The roller can also be used to apply a potential to the substrate. In an embodiment, this potential can be grounded relative to the counter electrode. Cheng Yaodong has a different composition. This depends on the pillars of the layer being deposited. Examples of useful electrolytic solutions are discussed above. The different layers of the field energy battery or the substrate may take the form of a continuous substrate on which deposition is to be performed and 147727.doc • 21· 201042094 2 may serve as one of the electrodes of the system. Different substrates can be used. Examples of different types of electrodes and the need for flute are discussed above; ^ The substrate can also be taken care of. The suspend coating is in the form of a TCO (which acts as an electrode). In a solid embodiment of the topsheet, the substrate is in the embodiment of the glass sheet, the glass is continuously referenced to FIG. 5, and between the substrate and the counter electrode 51? The gap between the two Ή 4 β m 隹亥两个 two of the solution, also / can be limited by the surface tension of the fluid "7, P, one of the electrolyte expansion has sufficient flow, very close enough to the right - & side guide The surface tension of the fluid is not additionally sealed to suppress the solution, and in addition, the overflow passage 545 can be configured to contain any electrolyte (Figure Μ中Μ, 古^Τ,, '日日& Flow channel 'but a cautious r::::r ...... side..., or depending on the heart. If the surface tension is not enough to be used: - Look at the main: pressure can be applied under the pressure of the seal. So, a Embodiments are as described above = one or more (four) pieces of n such seals are configured to direct the flow of liquid to maximize contact with the substrate during electrodeposition and minimize contact with the substrate The amount of electrolyte required to supply the continuous electrolyte. For example, one or more The dense 4+ can be used in the seal to suppress the electrolytic solution in the electric ore zone, and different mechanisms can be used for this suppression. For example, one or more sleeves of the counter electrode can be used in the field (five) Around the side, on the manifold body or in close proximity to the manifold body, for example, as described in relation to the manifold 147727.doc • 22· 201042094 material or hereinafter described with respect to the sealing element The materials are made bad enough to achieve a sufficient seal to aid in fluid suppression. In some embodiments, one or the other seal is attached to or in close proximity to the flow manifold and the counter electrode In another embodiment, the one or more seals are part of an integral manifold body.

G 〇諸多不同材料可用於此抑制目的。在—個實施例中，該一.個或多個密封件包含PTFE、㈣氧、了基橡膠及諸如 Vitcm 及 Kalrez(Vit〇n 及 Kakez 係 Dup〇nt p抓職⑽ astomers’ ofWllmingt〇n，之註冊商標）等含氟彈性體中之至少一者。出於某些實施例之目的之「密封件」無需與基板接觸。 ^ 由於反電極與基板彼此極接近，且電解液流動及表 2張力可用以補償電極之間的空間之週邊周圍之電解液損 :因此「密封件」可用以幫助抑制，而未必完全將電解封P制於電極之間。因此’密封件可係非接觸及接觸型密件，亦即’其巾基板不觸碰密封件或基板確實觸碰密封近二-個實施例中，非接觸密封件係場，其中基板極接 '密封件，舉例而言，約為幾毫米至一毫米或小於一毫板之^不觸碰該等密封件。此極接近無需要求密封件及基面之實際重疊，亦即，可僅使密封件及基板中且者之邊緣極接近以便最小化其等之間的電解液損失。並其他mir件緣示為具有一矩形（或正方形）剖面。在實始 P中’本發明不可以此方式而受到限定。在—個例中，密封件在密封件之接觸或極接近於基板之若干 147727.d〇c -23- 201042094 部分處具有最小表面面積(舉例而言一「淚滴」形、三角形：鰭形或刃形剖面)。當基板與基板接觸時，可挑選材料、不僅保4基板文到損害而且保護電沉積之材料。如下文更詳細地闡述，某些實施例包含一個或多個接觸及/ 或非接觸密封件。圖6繪示根據本發明之一具有一本體605 個實施例之一流動歧管600，其一反電極610、分別係615及620之電解液入口及出口，以及該反電極之任—側上之密封件63〇。在電沉積期間，基板625在由虛線箭頭所指示之方向上移動。雖然圖6中未按比例顯示’但通常，該基板將跨過密封件㈣。若密封件㈣係接觸密封件，則該基板將觸碰該等密封件；若係非接觸密封件，則該基板將極靠近該等密封件（如上所述），但不觸碰該等密封件。在存在該基板與該等密封件之重疊之情形τ，且因此阻檔電沉積，則可在了稍後階段修剪掉該基板之此部分。由於此圖未按比例繪製’-熟習此項技術者將瞭解’料電極可係彼此極靠近且因此密封件630可係相當薄，舉例而言，約為小於一毫米約毫米至幾毫米厚（在該等電極之間的維度上）。另-實施例係-種如上所述之裝置，其中該一個或多個密封件經組態以在該基板之平行於電解液流動之方向之側中之每一者上形成一流動障壁，且在該流動歧管之下游端上形成一部分流動障壁。圖7繪示一流動歧管7〇〇，其具有一本體705、一反電極710、一電解液入口 715及在此實例中跨過該&電極之週邊之三個㈣之一密封件72〇。在電沉 147727.doc -24- 201042094 積期間，基板（未繪示）在由虛線箭頭所指示之方向上（亦即’平行於该反電極）且在自该歧管之入口端至該歧管之相對端之一方向上移動。在此實例中，該基板將跨過密封件720之長度及寬度（或在邊緣型非接觸密封之情形下靠近於寬度）。密封件720，無論是否係接觸型，皆有助於將電解液抑制於該等電極之間及密封件72〇之三個側内之體積中。密封件720可係該歧管之整體本體之部分或附接至〇其。在此實例中，密封件720中之孔口 725充當電解液出口。在一個實施方案中，歧管700係一電沉積裝置之部为，其中歧管7 00係垂直地（或以大於零之某一角度）定向，亦即，其中該電解液入口在該歧管之頂部處且孔口 725在其底部處以使得重力可用以幫助電解液含有（防止該電解液向該入口成動）且在該等電極之間流動（重力將電解液向下拉動）。在此組態中，如上所述，電解液將以一大致層流方式在該等電極之間流動。另一實施例係如相對於圖7 〇所述之裝置，其進一步包含在該流動歧管之上游端上形成一流動障壁之一上游密封件，其中電解液入口位於該上游密封件之下游。如以上所提及，在某些實施例中，存在有助於充分抑制電解液以在電沉積期間維持所期望之流動特性之一個或多個密封7〇件。在某些實施例中，此配置包含經由接觸及/ 或非接觸密封件密封反電極周圍之一週邊。因此，一個實施例係一種如上所述之電沉積裝置，其中一個或多個密封件經組態以在該流動歧管及基板與該一個或多個密封件嚙 I47727.doc -25- 201042094 個或多個密封件時在該基板與該流動歧門兮㈣體積）。在—個實施例中，在電沉積期間個r解液入口及-電解液出口各自含有於該室内。在一個實施例中，經由—單個密封件建立該週邊，其"單㈣封件係—接觸及/或—非接觸型㈣件。亦即，該\ 個检封件可具有接觸該基板之若干部分及不接觸該基板之右干部分，此取決於該系統之流動及其他要求。舉例而 § ’該早個密封件可係、矩形、橢圓形、圓形或任-適合形狀。該單個密封件可附接至該流動歧管及該反電極中之至少一者或不附接至任—去。/ ^ |纟一個實施例中，該單個密封實例，該單個密封件係矩形件經組態以週期性地在電鍍作業之間移除，以有助於在電沉積之間保持該室清潔。該密封件被清潔以進一步使用或由-新密封件替換。在一個實施例中，如圖Μ中所繪示之圖8A緣不本發明之—實例性電沉積總成綱之一分解圖:粗雙頭箭頭指示該總成之個別組件在電沉積期間如所扣不嚙合。為簡明起見，未繪示諸如控制器、電壓線、流體流動線、幫浦、儲液槽等組件。總成咖包含—流動歧管805’如上文相對於其他實施例所述，流動歧管_具有 -電解液入口及出口以及一反電極。虛線箭頭指示電解液自該入口 ’跨越該反電極且經由該出口排出之既定流動型樣。總成800亦包含—矩形密封件81〇、一連續基板8丨5及 -輥820。虛線箭頭亦指示該基板及嚙合且移動該基板之輥之既定移動型樣。此等組件可如上文相對於其他實施例 147727.doc -26- 201042094 所述發揮作用’但下文更詳細地闡述此實施例之細節。 Ο Ο 圖8Β繪示其中嚙合圖8 Α中所繪示之組件之總成8〇〇。歧管805具有一本體8〇1，其包含反電極8〇2及在電沉積期間供電解液進入及退出該系統之入口 803及出口 8〇4。密封件 810在與基板815及歧管8〇5嚙合時形成一體積（室），其在此實例中涵蓋該反電極及電解液入口埠及出口埠之週邊。因此，一旦嚙合且電解液正在流動，即在該基板（電極）與反電極之間建立電解液之一層流流動。此外，如相對於圖6 所提及，該繪示未按比例，舉例而言，該等電極之間的距離了係相▲小且相應地密封件8 1 〇可係小於一毫米至約為數毫米厚。並且，舉例而言，該密封件之剖面可係一刀形、三角形或淚滴形而非矩形，且舉例而言，該密封件之 '悤形狀可係橢圓形、菱形或其他多邊形或非規則形狀而非矩形’此取決於所期望之流動特性。 =次相對於圖8八及犯參考實施例，密封件81〇可係一接觸雄封件、#接觸密封件或該兩者之—組合。在一個實施例中’该週邊密封件係、如上所述之—接觸密封件（有時稱為-軟密封件），其在該密封件之整個週邊周圍實現與 4基板之接觸H實施例中，該週邊密封件係如上所乂 .，屯非接觸密封件，其中不與該基板實際接觸而是足夠靠近該基板，在電沉積期間，除表面張力及流動速率之外，該基板與較電極之間總存在足以達成均自膜沉積之電解液I X實施例中，密封件具有接觸及非接觸舉例而° ’其中基板在平行於該基板之移動方向之 U7727.doc -27· 201042094G 诸多 A variety of different materials can be used for this suppression purpose. In one embodiment, the one or more seals comprise PTFE, (tetra) oxygen, base rubber, and such as Vitcm and Kalrez (Vit〇n and Kakez Department Dup〇nt p) (10) astomers' of Wllmingt〇n, At least one of a fluorine-containing elastomer such as a registered trademark). The "seal" for the purposes of some embodiments need not be in contact with the substrate. ^ Since the counter electrode and the substrate are in close proximity to each other, and the electrolyte flow and the tension in Table 2 can be used to compensate for the electrolyte loss around the periphery of the space between the electrodes: the "seal" can be used to help suppress, and the electrolytic seal may not be completely P is made between the electrodes. Therefore, the 'sealing member can be a non-contact and contact type dense member, that is, 'the towel substrate does not touch the seal or the substrate does touch the seal. In the second embodiment, the non-contact seal is a field, wherein the substrate is connected to the end. The seals, for example, are on the order of a few millimeters to one millimeter or less than one millimeter without touching the seals. This is extremely close to the fact that the actual overlap of the seal and the substrate is not required, i.e., only the edges of the seal and the substrate are brought into close proximity to minimize electrolyte loss between them. And other mir pieces are shown as having a rectangular (or square) profile. In the actual P, the present invention is not limited in this way. In one example, the seal has a minimum surface area at the portion of the seal that is in contact with or in close proximity to the substrate 147727.d〇c -23- 201042094 (for example, a "teardrop" shape, a triangle: a fin shape Or blade profile). When the substrate is in contact with the substrate, materials can be selected, not only to protect the substrate but also to protect the material of electrodeposition. As explained in more detail below, certain embodiments include one or more contact and/or non-contact seals. 6 illustrates a flow manifold 600 having a body 605 embodiment, a counter electrode 610, electrolyte inlets and outlets for 615 and 620, respectively, and any side of the counter electrode. The seal 63〇. During electrodeposition, substrate 625 is moved in the direction indicated by the dashed arrow. Although not shown to scale in Figure 6, 'typically, the substrate will span the seal (4). If the seal (4) contacts the seal, the substrate will touch the seal; if it is a non-contact seal, the substrate will be very close to the seal (as described above), but the seal is not touched Pieces. In the presence of the overlap of the substrate with the seals τ, and thus the barrier electrodeposition, this portion of the substrate can be trimmed at a later stage. Since this figure is not drawn to scale '- it will be appreciated by those skilled in the art that the electrodes can be in close proximity to one another and thus the seal 630 can be relatively thin, for example, less than about one millimeter and about millimeters to a few millimeters thick ( In the dimension between the electrodes). A further embodiment is the apparatus as described above, wherein the one or more seals are configured to form a flow barrier on each of the sides of the substrate parallel to the direction of electrolyte flow, and A portion of the flow barrier is formed on the downstream end of the flow manifold. 7 illustrates a flow manifold 7A having a body 705, a counter electrode 710, an electrolyte inlet 715, and in this example three (four) one seals 72 spanning the periphery of the & electrode. Hey. During the sinking of 147727.doc -24- 201042094, the substrate (not shown) is in the direction indicated by the dashed arrow (ie, 'parallel to the counter electrode) and from the inlet end of the manifold to the difference Move in the direction of one of the opposite ends of the tube. In this example, the substrate will span the length and width of the seal 720 (or near the width in the case of an edge type non-contact seal). The seal 720, whether or not it is in contact, helps to inhibit the electrolyte from being trapped within the volume between the electrodes and the three sides of the seal 72. Seal 720 can be part of or attached to the integral body of the manifold. In this example, the orifice 725 in the seal 720 acts as an electrolyte outlet. In one embodiment, the manifold 700 is part of an electrodeposition apparatus wherein the manifold 700 is oriented vertically (or at an angle greater than zero), that is, wherein the electrolyte inlet is in the manifold At the top and the orifice 725 is at its bottom so that gravity can be used to help the electrolyte contain (prevent the electrolyte from moving into the inlet) and flow between the electrodes (gravity pulls the electrolyte downward). In this configuration, as described above, the electrolyte will flow between the electrodes in a substantially laminar flow. Another embodiment is the apparatus as described with respect to Figure 7A, further comprising forming an upstream seal on one of the flow barriers on the upstream end of the flow manifold, wherein the electrolyte inlet is located downstream of the upstream seal. As mentioned above, in certain embodiments, there are one or more seals that help to substantially inhibit the electrolyte to maintain the desired flow characteristics during electrodeposition. In certain embodiments, this configuration includes sealing one of the perimeters around the counter electrode via a contact and/or non-contact seal. Accordingly, an embodiment is an electrodeposition apparatus as described above, wherein one or more seals are configured to engage the flow manifold and substrate with the one or more seals I47727.doc -25- 201042094 Or a plurality of seals on the substrate and the flow threshold (four) volume). In one embodiment, the r solution inlet and the electrolyte outlet are each contained in the chamber during electrodeposition. In one embodiment, the perimeter is established via a single seal, which "single (four) seal is a contact and/or - non-contact type (four) piece. That is, the \ seals may have portions that contact the substrate and do not touch the right stem portion of the substrate, depending on the flow of the system and other requirements. For example, the earlier seal may be tied, rectangular, elliptical, circular or any-suitable. The single seal can be attached to or not attached to at least one of the flow manifold and the counter electrode. / ^ | 纟 In one embodiment, the single seal example, the single seal is rectangular configured to be periodically removed between plating operations to help keep the chamber clean between electrodepositions. The seal is cleaned for further use or replaced by a -new seal. In one embodiment, FIG. 8A, as illustrated in FIG. 8A, is not an exploded view of an exemplary electrodeposition assembly: the thick double-headed arrows indicate individual components of the assembly during electrodeposition, such as The buckle does not engage. For the sake of brevity, components such as controllers, voltage lines, fluid flow lines, pumps, reservoirs, etc. are not shown. The assembly coffee contains a flow manifold 805' as described above with respect to other embodiments, the flow manifold_ has - electrolyte inlet and outlet and a counter electrode. The dashed arrow indicates the predetermined flow pattern from the inlet 'crossing the counter electrode and exiting through the outlet. Assembly 800 also includes a rectangular seal 81A, a continuous substrate 8丨5, and a roller 820. The dashed arrows also indicate the intended movement pattern of the substrate and the rollers that engage and move the substrate. Such components may function as described above with respect to other embodiments 147727.doc -26- 201042094', but the details of this embodiment are set forth in greater detail below. Β Ο Figure 8Β shows the assembly 8〇〇 in which the components shown in Figure 8 are engaged. Manifold 805 has a body 8〇1 that includes a counter electrode 8〇2 and an inlet 803 and an outlet 8〇4 for the electrolyte to enter and exit the system during electrodeposition. Seal 810 forms a volume (chamber) when engaged with substrate 815 and manifold 8A5, which in this example encompasses the periphery of the counter electrode and electrolyte inlet and outlet ports. Therefore, once meshed and the electrolyte is flowing, a laminar flow of electrolyte is established between the substrate (electrode) and the counter electrode. Moreover, as mentioned with respect to FIG. 6, the drawing is not to scale, for example, the distance between the electrodes is ▲ small and correspondingly the seal 8 1 〇 can be less than one millimeter to about Millimeter thick. Also, for example, the cross-section of the seal may be a knife-shaped, triangular or teardrop-shaped rather than a rectangular shape, and for example, the '悤 shape of the seal may be elliptical, diamond-shaped or other polygonal or irregular shape. Instead of a rectangle 'this depends on the desired flow characteristics. With respect to Figure 8 and the reference embodiment, the seal 81 can be a contact with a male seal, a #contact seal, or a combination of the two. In one embodiment, the peripheral seal is, as described above, a contact seal (sometimes referred to as a -soft seal) that achieves contact with the 4 substrate around the entire perimeter of the seal. The peripheral seal is a non-contact seal as described above, wherein the substrate is not in actual contact with the substrate but is sufficiently close to the substrate, and the substrate and the electrode are removed during electrodeposition in addition to surface tension and flow rate. There is always an electrolyte solution IX sufficient to achieve uniform deposition from the film. The seal has contact and non-contact examples. The substrate is in a direction parallel to the direction of movement of the substrate. U7727.doc -27· 201042094

側上與密封件810接觸，但在密封件810之上游及下游側處不接觸密封件801。在此實施例之一個實施方案中，密封件810之高度（或在該等電極之間所量測之維度上之厚度）在該上游及下游側處小於其在平行於該移動方向之側處。在另一實施例中，該基板在平行於該基板之移動方向之側上不與密封件81〇接觸，但在密封件81〇之上游及下游側處不接觸密封件801。在此實施例之一個實施方案中，密封件 81〇之高度（或在該等電極之間所量測之維度上之厚度）係大致均勻，但該基板僅觸碰該上游及下游側（舉例而此乃因該基板與該週邊密封件相比之有限寬度。雖然將密封件81叫示為與該歧管分離，但其可係該歧官之部分，舉例而言，形成為自一整體流動歧管本體伸出之一特徵且因此可被視為—流體壩。在不與該基板唾合 (接觸或不接觸）之情形T ’該流動電解液將在_之頂部邊緣上方流動。在一非接觸密封件之情形下，該基板剛好 =於該壩之頂部表面上方（或如該基板與密封件邊緣極The side is in contact with the seal 810, but does not contact the seal 801 at the upstream and downstream sides of the seal 810. In one embodiment of this embodiment, the height of the seal 810 (or the thickness in the dimension measured between the electrodes) is less at the upstream and downstream sides than at the side parallel to the direction of movement. . In another embodiment, the substrate is not in contact with the sealing member 81 on the side parallel to the moving direction of the substrate, but does not contact the sealing member 801 at the upstream and downstream sides of the sealing member 81. In one embodiment of this embodiment, the height of the seal 81 ( (or the thickness in the dimension measured between the electrodes) is substantially uniform, but the substrate only touches the upstream and downstream sides (for example) This is due to the limited width of the substrate compared to the perimeter seal. Although the seal 81 is referred to as being separate from the manifold, it may be part of the profile, for example, formed as a whole The flow manifold body extends one feature and can therefore be considered a fluid dam. The flow electrolyte will flow over the top edge of the _ in the absence of salvation (contact or non-contact) with the substrate. In the case of a non-contact seal, the substrate is just above the top surface of the dam (or as the substrate and seal edge

重叠那樣接近)且距其(舉例而言)少至幾毫米、一毫未或甚 $ /j、v|^ 使得因此僅最少之電解液自形成於該專電極之問& 4「 … 之間的該室」及該壩(内)溢出。諸如此之組態可係期望的，舉例而言，此之板流動，/ ι 〃、最^之電解液遠離該基動特別係在#近於電鑛表面之其干擾均勻電鑛之週邊之區中4 + 中Ά。在1亥等密封件係一拯艏密封件(舉例而言，鐵氟龍)之情形下，必須、主二：觸不會研磨性地損宝、/心Μ饴封件亥基板。此外，該等密封件即使係接觸 147727.doc -28· 201042094 型松封件亦可具有經組態以幫助電解液流動型樣（舉例而言，以幫助在該等電極之間建立大致層流流動）之穿孔或出口。在-個實施例中’該週邊密封件中存在孔口，如圖 7中所纷示之實例，其中該等孔口位於_個或多個側（舉例而§，平行於基板移動之方向之兩個側及/或該密封件之下游端側)上。此等孔口可用以使電解液流動型樣適合使用者以一特定方式電沉積一特定骐之需要。 Ο ❹ *雖然圖8B中將密封件81叫*為接觸該基板及該流動歧營兩者，但情況未必如此。出於本發明之目的之「喃合」包含極接近嗜合而沒有實際接觸。與如上文相對於該密封件之一表面與該基板之相對定位所述之非接觸密封一樣，非接觸密封亦可存在（單獨地或與基板㈣組合）於該密封件之一表面與該歧管之間。在一個實施例中，密封件刚係一剛性密封件（舉例而言，由鐵氟龍、ρΕΕκ、鐵氣龍塗佈之金屬（或其他支樓基礎結構）元件及諸如此類製成），其在。齒合期間懸置於該基板與該流動歧管之間。由於該密封件之一表面極接近於該歧管且該密封件之另一表面（或部刀右（舉例而s )该密封件具有一橢圓形或圓形剖面）極接近於該基板，因此即使在該密封件與該基板及該密封件與該歧管中之每一者之間的小間隙之間存在某一電解㈣漏’亦形成如上所述之體積或室。此一配置可（舉例而如上所述接近基板邊緣但亦在該反電極之邊緣處產生一期望之流動動態以增強均勻電鍍。此—組態亦可有利於幫助防止將原本將沉積之材料堆積於（舉例而言）一密封件與歧 147727.doc -29- 201042094 g表面相接之角落中。並且，此等組態係有到的，此乃因不/、該歧S或基板實體接觸（在此實例中，懸置於該基板與該歧管之間）之—密封件可易於互換及週期性地清潔。雖然圖8轉示該基板與該㈣件㈣㈣件之前導邊緣及該基板將在其上具有—沉積膜（此處未㈣）之後隨邊緣兩者處之大致相同層級處接觸，但該密封表面相對於該基板之此配置並非必需。在—個實施例中，在後隨邊緣處之密封表面低於前導邊緣處之密封表面，以補償必須在該密封件之後隨邊緣上方通過之該基板上之新沉積膜之厚度。在個實知例中，此差分高度並非必需，此乃因該密封件係易撓的且不損害該基板或沉積膜，舉例而言，一軟刀式密封件、彈性及/或彈簧致動密封件。如所提及，一個實施例係接觸及非接觸密封件之一組合。在此組合之一個實施方案中，該密封件之前導邊緣可係一接觸密封件而後隨邊緣係一非接觸密封件，其十新沉積膜不與該密封件之後隨邊緣接觸。一熟習此項技術者將瞭解，可在不背離本發明之範疇之情形下進行諸多組合。圖8B及圖9繪示呈一垂直定向之電沉積總成。此一定向允許重力幫助產生自該歧管之入口側至其出口側之—層流流動（向下）。然而，如上文所論述，該電沉積襄置之實施例並不限於任一特定定向。圖9繪示類似於相對於圖8A及8B所述之電沉積總成之另一電沉積總成900之一剖面圖，但電解液入口及出口具有不同組態。總成900包含具有一本體905及一反電極㈣之 147727.doc -30- 201042094 一歧官。如上所述，基板920由輥930驅動過該反電極。在此實例t ’密封件915在其前導側中具有一個或多個孔口 930且在其下游側中具有一個或多個孔口 935。一個或多個孔口 930充當電解液入口，且孔口们5充當自該基板與該反電極之間退出的電解液退出口。該等孔口與適當管道（未繪不）流體連通。此組態有助於藉由大致平行於該基板及該反電極之平面定向人口及出口流動來產生—大致層流流The overlap is as close as possible and is, for example, as small as a few millimeters, one millisecond or even $/j, v|^ such that only a minimum of electrolyte is formed from the problem of the special electrode & The room between the room and the dam (inside) overflows. Configurations such as this may be desirable, for example, the flow of the plate, / ι 〃, the most electrolyte away from the base motion, especially near the surface of the electric ore that interferes with the uniform electric ore. 4 + in the district. In the case of a seal such as 1 hai, which is a life-saving seal (for example, Teflon), it must be, the main two: the touch will not grind the damage, / heart Μ饴 seal. In addition, the seals may have a configuration to aid in the flow pattern of the electrolyte, even if it is in contact with the 147727.doc -28. 201042094 type loose seal (for example, to help establish a general laminar flow between the electrodes). Perforation or outlet of flow). In one embodiment, there are apertures in the perimeter seal, as exemplified in Figure 7, wherein the orifices are located on one or more sides (for example, §, parallel to the direction of substrate movement) On both sides and/or on the downstream end side of the seal). These orifices can be used to adapt the electrolyte flow pattern to the needs of the user to electrodeposit a particular crucible in a particular manner. Ο ❹ * Although the seal 81 is called * in contact with the substrate and the flow ambiguity in Fig. 8B, this is not necessarily the case. "Blanching" for the purposes of the present invention involves very close to incompatibility without actual contact. As with the non-contact seal as described above with respect to the relative positioning of one of the surfaces of the seal with the substrate, a non-contact seal may also be present (alone or in combination with the substrate (4)) on one of the surfaces of the seal and the Between the tubes. In one embodiment, the seal is just a rigid seal (for example, made of Teflon, ρΕΕκ, Teflon coated metal (or other branch infrastructure) elements, and the like), . The substrate is suspended between the substrate and the flow manifold during the toothing. Since one surface of the seal is in close proximity to the manifold and the other surface of the seal (or the right knife (for example, s) has an elliptical or circular cross section) is in close proximity to the substrate, Even if there is a certain electrolysis (4) leak between the seal and the substrate and the small gap between the seal and each of the manifolds, a volume or chamber as described above is formed. Such a configuration may, for example, approach the edge of the substrate as described above but also create a desired flow dynamic at the edge of the counter electrode to enhance uniform plating. This configuration may also help to prevent the deposition of material that would otherwise be deposited. For example, a seal is in the corner that meets the surface of the 147727.doc -29- 201042094 g. And, these configurations are available because the / or the substrate physical contact (in this example, suspended between the substrate and the manifold) - the seal can be easily interchanged and periodically cleaned. Although Figure 8 shows the substrate and the (four) (four) (four) pieces of leading edge and the substrate It will be contacted at approximately the same level at both edges after having a deposited film (not (four) here), but this configuration of the sealing surface relative to the substrate is not necessary. In one embodiment, after The sealing surface at the edge is lower than the sealing surface at the leading edge to compensate for the thickness of the newly deposited film on the substrate that must pass over the edge after the seal. In a practical example, this differential height is not required This is because the seal is flexible and does not damage the substrate or deposited film, for example, a soft knife seal, an elastic and/or spring actuated seal. As mentioned, one embodiment is A combination of one of the contact and non-contact seals. In one embodiment of the combination, the leading edge of the seal can be a contact seal followed by a non-contact seal along the edge, and the new deposited film does not seal with the seal. The article is then contacted by the edge. It will be appreciated by those skilled in the art that many combinations can be made without departing from the scope of the invention. Figures 8B and 9 illustrate an electrodeposition assembly in a vertically oriented orientation. Gravity is allowed to help create laminar flow (downward) from the inlet side of the manifold to its outlet side. However, as discussed above, embodiments of the electrodeposition apparatus are not limited to any particular orientation. A cross-sectional view of another electrodeposition assembly 900 similar to the electrodeposition assembly described with respect to Figures 8A and 8B, but with different configurations of the electrolyte inlet and outlet. The assembly 900 includes a body 905 and a counter electrode (four) 147727.doc -30- 201042094 A submarine. As described above, the substrate 920 is driven by the roller 930 past the counter electrode. In this example, the 'seal 915 has one or more apertures 930 in its leading side and There are one or more orifices 935 in the downstream side. One or more orifices 930 serve as electrolyte inlets, and the orifices 5 act as electrolyte outlets exiting between the substrate and the counter electrode. In fluid communication with a suitable conduit (not shown). This configuration facilitates the generation of a substantially laminar flow by directing population and outlet flow substantially parallel to the plane of the substrate and the counter electrode.

Ο 動。相對於本文中之該入口及出口係該流動歧管之部分之說明，此係一致的，此乃因（舉例而言）密封件915可具有係 "亥心動歧I之整體本體之部分之類型。在其他實施例中’-密封元件與一歧管本體之組合(或嚙合)一同係該流動歧管之部分。如所提及’根據本發明之實施例之電沉積裝置之該密封件組件、該電解液人口或出σ及該歧管本㈣不限於任一特定幾何形狀。在具有—週邊型密封件之實施例中，舉例而言，該密封件可係矩形、橢圓形、圓形、正方形、三角形或-不規則形狀且具有係（舉例而言）矩形、圓形、糖圓形、淚滴形、三角形、不規則（亦即，任一適合形狀）之一 ❹。並且如所提及，本發明之一個態樣係在電沉積期間在該基板與反電極之間產生大致層流電解液流動。在本發明之裝置中，舉例而言，可經由對該密封件、電解液入口二等中之一者或多者之組態之操縱以及利用表面張力、重力、電解液之特性(舉例而言，勘度、溫度及Μ力）來達成流動特性。、 147727.doc -31. 201042094 圖10繪示本發明之另一電沉積總成1000之一透視圖，其中密封件及電解液埠經組態以幫助在該基板與反電極之間形成大致層流電解液流動。總成1000包含具有一本體丨005 及一反電極1010之一歧管。如上所述，基板1030(圖中顯不在該歧管上方）由輥（未繪示）驅動過該反電極，且基板 1030跨過密封件1〇25之寬度或至少極接近（舉例而言，基板與密封件重疊或不重疊之非接觸密封）。在此實例中，密封件1025具有一六邊形形狀（及一矩形剖面）^電解液入口 1015及電解液出口 1〇2〇如所繪示係三角形但可係矩形、圓形、橢圓形及類似形狀。密封件1〇25之六邊形形狀幫助藉由經由最接近該入口之成角度側自該入口平滑地導引電解液流動以在該基板與反電極之間朝向下游出口擴展及偏轉來產生一大致層流流動。舉例而言，亦可藉由使用流動引入及/或自（舉例而言）如相對於圖9所述之室退出電解液之入口及/或出口（亦即，平行於電極表面）來在裝置 1000中產生層流流動，以便避免自一垂直入口轉向至一水平流動（如圖1 〇 t所繪示）。該密封之另一實施方案係其中將該基板（舉例而言― 泊基板）之邊緣彎曲以使得其含有電解液，而不觸碰該反電極及導致—短路。在此實施方案中，在製造太陽能電池堆疊之後，箔之被彎曲區域將極可能必須被修剪且丟棄。此兩個實例（不同密封件且使用該基板之一部分作為垂直密封兀件）僅係在該基板上之沉積期間用於抑制電解液之裝置組件及方法之說明性非限定性實例。 147727.doc •32- 201042094 另一實施例係一種用於將一電鍍溶液遞送至一基板之表面之流動歧管，該流動歧管包含：⑴一電解液入口，該電解液入口在以下位置之之上游處；（ii)一反電極，該反電極安置於該流動歧管之一表面上；及（iii)一電解液出口，該電解液出口在該反電極之下游；其中該流動歧管經組態以在該反電極與該基板之一表面之間自該電解液入口供應該電鍍溶液之一連續流動，以使得電鍍可發生於該基板之該表面上，且然後經由該電解液出口排出。在一個實施例 ° 中，該流動歧管經組態以在與一連續片基板嚙合之同時供應電解液。在另一實施例中，該流動歧管進一步包含一控制器’其經組態以在該連續片基板極接近於該反電極地連續移動過該反電極之同時向該連續片基板供應該電鍍溶液之該連續流動。在另一實施例中，該流動歧管經組態以在該基板之該表面與該反電極之間產生該電鍍溶液之一大致層流流動或一紊流流動。該流動歧管亦可包含一個或多個〇密封件’其經組態以引導電鍍溶液之流動以便在電沉積期間最大化與基板之表面之接觸且最小化產生接觸該基板之該電鑛溶液之連續流動所需之電鍍溶液之量。該流動歧管亦可包含用於收集已用電解液之一個或多個溢流通道。該個或多個密封件可經組態以在該基板之平行於電鍍溶液饥動之方向之側中之每一者上形成一流動障壁且在該流動歧管之下游端上形成一部分流動障壁，且視情況包含在該 μ動歧管之上游端上形成一流動障壁之一上游密封件。因此在另實施例中’該一個或多個密封件經組態以在該 147727.doc -33- 201042094 流動歧管及該基板與該一冑或多冑密封件唾合時在該基板之該表面與該流動歧管之間形成一室或體積。在—個實施例中，該流動歧管具有一單個密封件。在一更具體實施例中，該密封件係矩形。歧管實施例亦可包含經組態以在電解液"IL動時但在電沉積未正在發生時再循環該電解液之幫浦及閥。亦即，其_該裝置經組態以使該電解液再循環經過該歧管直至電沉積開始為止且然後不再使已用電解液再循環經過該歧管，而是轉向以用於其他沉積（舉例而言，再構成）或轉向至一廢物流之一實施例。另一更具體實施例係一種用於在一連續基板上製造一光伏打電池之-電沉積裝置，該裝置包含：⑴-移動總成，其用於在電沉積期間將一基板定位於距一反電極約2出爪與約5 mm之間處；（ii)一流動歧管，其經組態以使一電解液在該基板與一反電極之間流動且連續地在該基板之電鍍表面與該反電極之間供應電解液；（iii)一驅動組件，其經組態以在電沉積期間在大致不彎曲該基板之情形下將該連續基板移動過該流動歧管及該反電極；及（iv) 一個或多個密封件，其經組態以引導電解液之流動以便最大化該連續基板之僅一電鍍側與該反電極之間的接觸；其中該反電極定位於6亥流動歧管上或係該流動歧管之一組成組件且該連續基板包括一導電材料及具有一導電塗層之一材料中之至少一者。上述實施例並不限於在（舉例而言）一連續基板上工作之單個裝置。一個實施例係一種包含如本文中逐次闡述之運 147727.doc -34 - 201042094 作於一單個連續基板上之流動歧管中之至少兩者之電沉積系統。圖11繪示用於在一基板上電沉積多個層之系統11〇〇。在此實例中，二個電沉積裝置1110、1120及丨130經配置以使得當基板1140自一個裝置傳遞至下一個時，在該基板上電沉積一第一層’然後在該第一層上沉積一第二層，且然後在該第二層上沉積一第三層。該連續基板可針對電沉積或 ❹ W他處理以不彳τ止或週期性地停止之方式移動經過裝置。在個實施例中，該基板連續地移動經過該等電沉積站中之每一者。在圖u中所繪示之實例中，第一、第二及第三層中之每一纟具有不同組成I因此使用不同電沉積化學品沉積。雖然繪示為相同，但沉積裝置111〇、112〇及113〇中之每一者可具有與如所述本發明一致之任一組態。根據本發明之實施例之電沉積裝置允許諸多優點，包含當在一單個基板上沉積多個層時之極度靈活性，亦即，其等係模組〇 <且可端視期望之結局而互換。舉例而言，不僅該等化學品可跨越不同的電沉積裝置而變化，而且個別裝置根據所述之變量（諸如，密封組態、形狀、接觸型或非接觸型、流動參數及諸如此類）而可係唯一（或非唯一在圖11中亦注意’如由該基板上方及下方之粗箭頭所指示，在沉積站中間（及在最後沉積站之後）可存在基板之新沉積層之預處理及後處理。亦即，可存在定位於電沉積裝 f中間（或在第-電沉積裝置之前）的其他裝置以（舉例而言）在基板進入第一站之前處理該基板（舉例而言，預加 147727.doc •35- 201042094 熱、預弄濕）或在一新添加膜進入一後續站之前處理該新添加臈（舉例而言，一烘乾步驟、一烘焙及/或退火步驟及個或多個介入層之一添加等）。亦可在該等電沉積站中間及/或之後對該等層執行計量。並且，由於可將個別電沉積裝置對準（舉例而言，如圖 11中所繪示）’因此可在多個裝置中處理該基板而不必彎曲該基板，此允許較高製程控制及膜穩定性及均勻性。— 旦完成期望之沉積，即進行基板之進一步後處理，舉例而吕，接著可切割基板以形成個別太陽能電池，然後可基於其等之效能測試且分類該等個別太陽能電池，隨後進行— 接合作業及一囊封作業以形成太陽能面板。可針對效率、開路電壓、短路電流及諸如此類測試該等太陽能電池。舉例而言，該等太陽能電池可根據其等效能特性進行分裝I 適當地用於製造太陽能面板。序列號為61/171,〇〇7之美國臨時申請案中闡述一連續基板上之連續型作業之進一步細節’該案出於所有目的以引用方式併入本文中。如—熟習此項技術者將瞭解，根據本發明之實施例之電沉積裝置亦可包含用於管理該系統之不同組件之一控制器系統。藉由舉例之方式，該控制器可經組態或程式化以選擇在基板與電極之間施加之電位差、控制電解液流動速率及流體管理、控制移動機構及諸如此類。可利用任一適合硬體及/或軟體來實施該控制器系統。舉例而言，該控制器系統可包含一個或多個微控制器及微處理器，諸如，可程式化器件（舉例而言，複雜可程式化邏輯器件（CPLD)及 147727.doc -36- 201042094 現場可程式化閘陣列（FPGA))及不可程式化器件（諸如，閘陣列專用積體電路（ASIC)或通用微處理器及/或記憶體，其經組態以儲存用於通用處理作業及/或本文中所述之發明性方法之資料、程式化指令）。另一實施例係一種電沉積方法’其包含：（i)在一基板之電鍍表面極接近於反電極之同時使用向該基板供應一電解液之一連續供應之一流動歧管來使電解液在該基板與該反電極之間流動；及（Π)在該基板與該反電極之間施加一電鑛電位；其中該反電極經組態以大致跨過該基板之至少一個維度且定位於該流動歧管上或係該流動歧管之一組成組件。圖12繪示用於此方法實施例之一製程流程丨2〇〇。首先，使用（舉例而言）如上所述之一流動歧管在一基板與一反電極之間建立一電解液流動，其中該基板與反電極係極接近 (如上文相對於本發明之裝置所述）（參見121〇)。然後，一電錢電位在該基板與反電極之間以便達成一種物質自該電解液至該基板之電沉積，參見122〇 ^然後，該製程流程結束。在一個實施例中，該方法進一步包含在電沉積期間將該基板連續地移動過該反電極，其中該基板包含一連續片’該連續片包含一導電材料及具有一導電塗層之一材料中之至少一者。在另一實施例中，該方法進一步包含：（iii)當基板係靜止時將材料電沉積至該基板上；（iv)重新定位該基板以便定位不具有電沉積材料之一區域以進行電沉積；及將材 147727.doc -37· 201042094 料電沉積至該區域上；其中該基板係包含一導電材料及具有一導電塗層之一材料中之至少一者之—連續片。在一個實施例甲，極接近意指在電沉積期間反電極與該基板定位為相隔約2 mm與約25 mm之間’在另—實施例中，在電沉積期間相隔約2 mm與约10 mm之間，且在另一實施例中，在電沉積期間相隔約2 mm與約5 mm之間。在又一實施例令’極接近意指該反電極與該基板定位為相隔約〗麵旬 mm之間。在另-實施例中，該反電極與該基板相隔約〇1 mm與約2醜之間。在—個實施例中，使—電解液在該基板與該反電極之間流動包含在該基板與該反電極之間產生該電解液之-大致層流流動或一蒼流流動。在—個實施例中，該流動係大致層流。在另一實施例中，該方法進一步包含採用經組態以引導電解液之流動以便在電沉積期間最大化與基板之接觸且最小化產生接觸該基板之電解液之連續供應所需之電解液之量之一個或多個密封件。在一更具體實施例中，該一個或多個密封件經組態以在流動歧管及基板與該-個或多個密封件嚙合時在該基板與該流動歧官之間形成-室(或體積)；該流動歧管進一步包含經組態以向該室供應電解解履之電解液入口及經組態以在電沉積期間將已用電解液自該室排出之一電解液出口。在另一實施例中，該一個弋夕+ 4·, 或夕個岔封件經組態以在該基板之平行於電解液流動方向相莉万向之側中之每一者上形成一流動障壁且在該流動歧管之下游端上形成—部分流動障壁，且視情況係在該流動歧管之上游端上形成-流動障壁之一上游 147727.doc •38· 201042094 密封件，其中該流動歧管進一步包含一電解液入口，該電解液入口位於該上游密封件之下游處。可將該等密封^附接至該流動歧管及該反電極中之至少一者。在室或體積實施例中，該一個或多個密封件包含一單個矩形密封件或如相對於以上裝置所述之一形狀之一密封件。本發明之某些實施例具有數個相關聯之優點。一個優點可係在維護費用方面低於習用電沉積裝置。舉例而言，在採用一連續基板之實施例中，該基板之僅一個表面與電解液接觸，且此配置顯著地減輕該等部件之化學相容性問題且亦顯著地降低裝備之成本。此裝備之維護較容易，此乃因該裝備之相對較小數目之部件曝露於苛性化學品。另一優點可係在化學品消耗方面低於習用系統。在一個實施方案中，顯著地減少該化學品消耗，此乃因僅液體之一薄膜用於沉積且基板之僅一個表面連同反電極與電鍍溶液接觸。又4 〇另-優點可係沉積均句性。由於電解液之—薄膜不斷地流過電極’因此可藉由補充在沉積製程期間所耗盡之化學品來達成一顯著更佳之化學均勻性。在一個實施方案中，舉例而言，可藉由製作比連續基板大之歧管電極（如圖5b 中所翁不之實例）來達成一大致平行板組態。此僅係用以達成此結果之一個可能配置。㈣施方案之諸多其他變化形式可達成-平行板組態。在所圖解說明之實例中，可極精確地控制基板溫度、電位及扁平度，此乃因基板與輕接觸。並且，可極精確地控制電解液之溫度，此乃因其係流 147727.doc -39· 201042094 動電解液之一薄膜且歸因於邊緣處之消散之熱量損失僅表不總液體體積之一極小百分比。優於省用裝置及方法之又一優點可係模組性及可互換性。某些實施方案極佳地適於模組性及可互換性。相同歧官及基礎結構可用於多個沉積，此乃因該等部件之化學相容性因僅弄濕該等電極而不成問題。此實施方案中之歧管大小可經調節而在一多個沉積線中達成最快沉積，且對於較長沉積，可使用多個歧管來達成目標厚度。上文相對於圖11闡述了關於模組性之其他優點。 ^本文令所述之電沉積裝置及方法之某些實施例（舉例而言，在連續基板上）克服與電化學沉積之習用方法相關聯之大多數挑戰，從而顯著地降低裝備之成本、減少化學品 /肖耗、增強可維護性、沉積均句性且其係模組性及可互換性。雖然已出於清晰理解之目的較詳細地闡述了前述發明，仁將明瞭’可在隨附巾請專利範圍之範相實踐某些改變及修改。因此’應將當前實施例視為說明性而非限制性，且本I明並不限於本文中給出之細節，而是可在隨附申请專利範圍之範疇及等效形式内進行修改。叫【圖式簡單說明】圖1緣示-太陽能電池光伏打堆疊結構之一剖面圖。圖2繪示一習用光伏打堆疊形成情景。圖3不用於太陽能電池製造之_習用電沉積裝置。圖4繪示根據本發明之實施例之一流動歧管之一透視 147727.doc -40- 201042094 圖。圖5 A及5B分別繪示根據本發明之實施例之一電沉積裝置之一剖面側視圖及正視圖。圖6繪示根據本發明之實施例之另一流動歧管之一透視圖。圖7繪示根據本發明之實施例之另一流動歧管之一透視圖。Ο. This is consistent with respect to the description of the inlet and outlet portions of the flow manifold herein, for example, because the seal 915 can have a portion of the integral body of the system Types of. In other embodiments, the combination of the sealing element and a manifold body (or meshing) is part of the flow manifold. As mentioned, the seal assembly of the electrodeposition apparatus according to the embodiment of the present invention, the electrolyte population or the σ and the manifold (4) are not limited to any particular geometry. In embodiments having a perimeter seal, for example, the seal may be rectangular, elliptical, circular, square, triangular or - irregular and have, for example, a rectangle, a circle, One of the sugar circles, teardrops, triangles, irregularities (ie, any suitable shape). And as mentioned, one aspect of the invention produces a substantially laminar electrolyte flow between the substrate and the counter electrode during electrodeposition. In the apparatus of the present invention, for example, manipulation of the configuration of one or more of the seal, electrolyte inlet, etc., and utilization of surface tension, gravity, electrolyte characteristics (for example, , survey, temperature and force) to achieve flow characteristics. 147727.doc -31. 201042094 FIG. 10 is a perspective view of another electrodeposition assembly 1000 of the present invention, wherein the seal and the electrolyte are configured to help form a substantially layer between the substrate and the counter electrode. The flowing electrolyte flows. Assembly 1000 includes a manifold having a body 005 and a counter electrode 1010. As noted above, the substrate 1030 (not shown above the manifold) is driven by the roller (not shown) through the counter electrode, and the substrate 1030 spans the width of the seal 1 〇 25 or at least very close (for example, Non-contact seal with or without overlapping of the substrate. In this example, the seal 1025 has a hexagonal shape (and a rectangular cross section). The electrolyte inlet 1015 and the electrolyte outlet 1〇2 are triangular in shape but can be rectangular, circular, elliptical, and Similar shape. The hexagonal shape of the seal 1 帮助 25 helps to create a smooth flow of electrolyte flow from the inlet via the angled side closest to the inlet to expand and deflect between the substrate and the counter electrode toward the downstream outlet. Rough laminar flow. For example, the device can also be introduced into and/or out of the electrolyte (for example, parallel to the electrode surface) by using a flow introduction and/or, for example, as described with respect to FIG. A laminar flow is created in 1000 to avoid diverting from a vertical inlet to a horizontal flow (as depicted in Figure 1 〇t). Another embodiment of the seal is in which the edge of the substrate (e.g., a mooring substrate) is bent such that it contains an electrolyte without touching the counter electrode and causing a short circuit. In this embodiment, after the solar cell stack is fabricated, the bent regions of the foil will most likely have to be trimmed and discarded. These two examples (different seals and using one portion of the substrate as a vertical sealing element) are merely illustrative non-limiting examples of device assemblies and methods for inhibiting electrolyte during deposition on the substrate. 147727.doc • 32- 201042094 Another embodiment is a flow manifold for delivering a plating solution to a surface of a substrate, the flow manifold comprising: (1) an electrolyte inlet, the electrolyte inlet being in the following position Upstream; (ii) a counter electrode disposed on a surface of the flow manifold; and (iii) an electrolyte outlet downstream of the counter electrode; wherein the flow manifold Configuring to continuously flow one of the plating solutions from the electrolyte inlet between the counter electrode and one of the surfaces of the substrate such that plating can occur on the surface of the substrate and then exit through the electrolyte discharge. In one embodiment, the flow manifold is configured to supply electrolyte while being engaged with a continuous sheet substrate. In another embodiment, the flow manifold further includes a controller configured to supply the plating to the continuous substrate while the continuous substrate is continuously moved past the counter electrode in close proximity to the counter electrode This continuous flow of the solution. In another embodiment, the flow manifold is configured to produce a substantially laminar flow or a turbulent flow of the plating solution between the surface of the substrate and the counter electrode. The flow manifold may also include one or more helium seals that are configured to direct the flow of the plating solution to maximize contact with the surface of the substrate during electrodeposition and to minimize the generation of the electromineral solution that contacts the substrate. The amount of plating solution required for continuous flow. The flow manifold may also include one or more overflow passages for collecting used electrolyte. The one or more seals can be configured to form a flow barrier on each of the sides of the substrate parallel to the direction in which the plating solution is hunted and form a portion of the flow barrier on the downstream end of the flow manifold And optionally forming an upstream seal of one of the flow barriers on the upstream end of the μ-manifold. Thus in another embodiment, the one or more seals are configured to be in the substrate when the 147727.doc-33-201042094 flow manifold and the substrate are spouted with the one or more seals A chamber or volume is formed between the surface and the flow manifold. In one embodiment, the flow manifold has a single seal. In a more specific embodiment, the seal is rectangular. The manifold embodiment may also include pumps and valves that are configured to recirculate the electrolyte during electrolysis and while the electrodeposition is not occurring. That is, the device is configured to recirculate the electrolyte through the manifold until the beginning of electrodeposition and then no longer recycle the used electrolyte through the manifold, but instead diverts for other deposition (for example, reconstituted) or turned to an embodiment of a waste stream. Another more specific embodiment is an electrodeposition apparatus for fabricating a photovoltaic cell on a continuous substrate, the apparatus comprising: (1) a moving assembly for positioning a substrate at a distance during electrodeposition The counter electrode is between about 2 claws and about 5 mm; (ii) a flow manifold configured to flow an electrolyte between the substrate and a counter electrode and continuously on the plating surface of the substrate Supplying an electrolyte between the counter electrode; (iii) a drive assembly configured to move the continuous substrate through the flow manifold and the counter electrode during electrodeposition without substantially bending the substrate; And (iv) one or more seals configured to direct the flow of the electrolyte to maximize contact between only one plated side of the continuous substrate and the counter electrode; wherein the counter electrode is positioned at 6 mile flow One or a portion of the flow manifold is assembled on the manifold and the continuous substrate includes at least one of a conductive material and a material having a conductive coating. The above embodiments are not limited to a single device operating on, for example, a continuous substrate. One embodiment is an electrodeposition system comprising at least two of the flow manifolds as described herein, 147727.doc-34 - 201042094, for operation on a single continuous substrate. Figure 11 illustrates a system 11 for electrodepositing multiple layers on a substrate. In this example, the two electrodeposition devices 1110, 1120 and 丨130 are configured such that when the substrate 1140 is transferred from one device to the next, a first layer 'on the substrate is then electrodeposited' and then on the first layer A second layer is deposited and then a third layer is deposited on the second layer. The continuous substrate can be moved past the device in a manner that does not stop or periodically stop for electrodeposition or processing. In one embodiment, the substrate is continuously moved through each of the electrodeposition stations. In the example illustrated in Figure u, each of the first, second, and third layers has a different composition I and thus is deposited using a different electrodeposition chemical. Although depicted as being identical, each of deposition devices 111, 112, and 113 can have any configuration consistent with the present invention as described. An electrodeposition apparatus in accordance with an embodiment of the present invention allows for a number of advantages, including extreme flexibility when depositing multiple layers on a single substrate, i.e., its system module < and can look at the desired outcome exchange. For example, not only can such chemicals vary across different electrodeposition devices, but individual devices can vary depending on such variables (eg, sealed configuration, shape, contact or non-contact type, flow parameters, and the like). Is unique (or not uniquely noted in Figure 11) as indicated by the thick arrows above and below the substrate, there may be pre-treatment of the new deposited layer of the substrate in the middle of the deposition station (and after the last deposition station) Processing. That is, there may be other devices positioned in the middle of the electrodeposition package f (or in front of the first electrodeposition device) to process the substrate, for example, before the substrate enters the first station (for example, pre-add 147727.doc •35- 201042094 hot, pre-wet) or treat the new addition enthalpy before a new addition film enters a subsequent station (for example, a drying step, a baking and/or annealing step and one or more One of the intervening layers is added, etc.) The metering may also be performed on the layers in and/or after the electrodeposition stations. Also, since the individual electrodeposition devices can be aligned (for example, Figure 11 Illustrated] 'The substrate can thus be processed in multiple devices without having to bend the substrate, which allows for higher process control and film stability and uniformity. - Once the desired deposition is completed, further post-processing of the substrate is performed, For example, the substrate can be cut to form individual solar cells, and then the individual solar cells can be tested and classified based on their efficacy, followed by a bonding operation and an encapsulation operation to form a solar panel. For efficiency, open circuit Such solar cells are tested for voltage, short-circuit current, and the like. For example, the solar cells can be packaged according to their equivalent energy characteristics, and are suitably used to manufacture solar panels. Serial number 61/171, USA Further details of a continuous operation on a continuous substrate are set forth in the provisional application, which is hereby incorporated by reference for all purposes. The device may also include a controller system for managing different components of the system. By way of example, The controller can be configured or programmed to select a potential difference applied between the substrate and the electrodes, control electrolyte flow rate and fluid management, control movement mechanisms, and the like. Any suitable hardware and/or software can be utilized to implement the Controller system. For example, the controller system can include one or more microcontrollers and microprocessors, such as programmable devices (for example, Complex Programmable Logic Devices (CPLD) and 147727.doc -36- 201042094 Field programmable gate array (FPGA)) and non-programmable devices (such as gate array dedicated integrated circuits (ASIC) or general purpose microprocessors and/or memory configured to be stored for A general processing operation and/or information, stylized instructions of the inventive method described herein. Another embodiment is an electrodeposition method comprising: (i) a plated surface of a substrate is in close proximity to the counter electrode Simultaneously supplying one of the electrolytes to the substrate to continuously supply a flow manifold to flow the electrolyte between the substrate and the counter electrode; and (Π) between the substrate and the counter electrode An electromineral potential is applied therebetween; wherein the counter electrode is configured to span substantially at least one dimension of the substrate and is positioned on or associated with one of the flow manifolds. FIG. 12 illustrates a process flow for one of the embodiments of the method. First, an electrolyte flow is established between a substrate and a counter electrode using, for example, a flow manifold as described above, wherein the substrate is in close proximity to the counter electrode system (as described above with respect to the apparatus of the present invention) (see 121〇). Then, a charge potential is between the substrate and the counter electrode to achieve electrodeposition of a substance from the electrolyte to the substrate, see 122, and then the process is completed. In one embodiment, the method further comprises continuously moving the substrate through the counter electrode during electrodeposition, wherein the substrate comprises a continuous sheet comprising a conductive material and a material having a conductive coating At least one of them. In another embodiment, the method further comprises: (iii) electrodepositing a material onto the substrate when the substrate is stationary; (iv) repositioning the substrate to position a region having no electrodeposited material for electrodeposition And electrically depositing material 147727.doc-37·201042094 onto the region; wherein the substrate comprises a conductive material and a continuous sheet having at least one of a material of a conductive coating. In one embodiment A, very close means that the counter electrode is positioned between the substrate and the substrate between about 2 mm and about 25 mm during electrodeposition. In another embodiment, between about 2 mm and about 10 apart during electrodeposition. Between mm, and in another embodiment, between about 2 mm and about 5 mm apart during electrodeposition. In yet another embodiment, 'very close' means that the counter electrode is positioned between the substrate and the substrate at a distance of about mm. In another embodiment, the counter electrode is spaced from the substrate by between about 1 mm and about 2 ug. In one embodiment, flowing the electrolyte between the substrate and the counter electrode comprises a substantially laminar flow or a convective flow of the electrolyte between the substrate and the counter electrode. In one embodiment, the flow is substantially laminar. In another embodiment, the method further comprises employing an electrolyte configured to direct the flow of the electrolyte to maximize contact with the substrate during electrodeposition and to minimize the continuous supply of electrolyte that contacts the substrate. One or more seals of the quantity. In a more specific embodiment, the one or more seals are configured to form a chamber between the substrate and the flow ambiguity when the flow manifold and substrate are engaged with the one or more seals ( Or a volume); the flow manifold further comprising an electrolyte inlet configured to supply an electrolysis solution to the chamber and an electrolyte outlet configured to discharge the used electrolyte from the chamber during electrodeposition. In another embodiment, the one of the + +, or the 岔岔 seal is configured to form a flow on each of the sides of the substrate parallel to the flow direction of the electrolyte a barrier and forming a partial flow barrier on the downstream end of the flow manifold, and optionally forming an upstream of one of the flow barriers on the upstream end of the flow manifold 147727.doc • 38· 201042094 seal, wherein the flow The manifold further includes an electrolyte inlet located downstream of the upstream seal. The seals can be attached to at least one of the flow manifold and the counter electrode. In a chamber or volumetric embodiment, the one or more seals comprise a single rectangular seal or a seal such as one of the shapes described above with respect to the above apparatus. Certain embodiments of the invention have several associated advantages. One advantage can be lower in maintenance costs than conventional electrodeposition devices. For example, in an embodiment employing a continuous substrate, only one surface of the substrate is in contact with the electrolyte, and this configuration significantly alleviates the chemical compatibility of the components and also significantly reduces the cost of the equipment. Maintenance of this equipment is relatively easy because a relatively small number of parts of the equipment are exposed to caustic chemicals. Another advantage may be lower in terms of chemical consumption than conventional systems. In one embodiment, the chemical consumption is significantly reduced because only one film of the liquid is used for deposition and only one surface of the substrate is in contact with the plating solution along with the counter electrode. Another 4 〇 Another - advantage can be deposited uniformity. Since the electrolyte-film continuously flows through the electrode', a significantly better chemical uniformity can be achieved by replenishing the chemicals that are depleted during the deposition process. In one embodiment, for example, a substantially parallel plate configuration can be achieved by making a manifold electrode that is larger than a continuous substrate (as in the example of Figure 5b). This is only one possible configuration to achieve this result. (d) Many other variations of the program can be achieved - parallel plate configuration. In the illustrated example, substrate temperature, potential, and flatness can be controlled with extreme precision due to the substrate being in light contact. Moreover, the temperature of the electrolyte can be controlled extremely precisely because it is one of the films of the 147727.doc -39· 201042094 kinetic electrolyte and the heat loss due to the dissipation at the edge is only one of the total liquid volumes. A very small percentage. Another advantage over the use of devices and methods is modularity and interchangeability. Certain embodiments are well suited for modularity and interchangeability. The same ambiguity and infrastructure can be used for multiple deposits because the chemical compatibility of the components is not a problem since only the electrodes are wetted. The manifold size in this embodiment can be adjusted to achieve the fastest deposition in a plurality of deposition lines, and for longer depositions, multiple manifolds can be used to achieve the target thickness. Other advantages regarding modularity are set forth above with respect to FIG. ^ Certain embodiments of the electrodeposition apparatus and methods described herein (for example, on a continuous substrate) overcome most of the challenges associated with conventional methods of electrochemical deposition, thereby significantly reducing the cost and equipment cost of the equipment. Chemical/distraction, enhanced maintainability, deposition uniformity and modularity and interchangeability. Although the foregoing invention has been described in more detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be made in the scope of the patent application. Therefore, the present embodiments are to be considered as illustrative and not restrictive, and the invention is not limited to the details of the invention. [Simplified description of the diagram] Figure 1 shows a cross-sectional view of a solar cell photovoltaic stacking structure. FIG. 2 illustrates a conventional photovoltaic stacking formation scenario. Figure 3 is not used in the manufacture of solar cells. 4 is a perspective view of one of the flow manifolds 147727.doc -40- 201042094, in accordance with an embodiment of the present invention. 5A and 5B are respectively a cross-sectional side view and a front elevational view, respectively, of an electrodeposition apparatus according to an embodiment of the present invention. 6 is a perspective view of another flow manifold in accordance with an embodiment of the present invention. Figure 7 is a perspective view of another flow manifold in accordance with an embodiment of the present invention.

圖8 A繪示根據本發明之實施例之一電沉積裝置之—分解圖8B繪示圖8A中之電沉積裝置之一側剖面圖。圖9繪示根據本發明之實施例之另一電沉積裝置之一側剖面圖。圖10繪示根據本發明之實施例之另一流動歧管之一透視圖。圖11續' 示根據本發明之實施例之包含多於一個電沉積裂置之一電沉積系統之一剖面圖。圖12繪示關於根據本發明之實施例之一電沉積方法之一製程流程。【主要元件符號說明】 100 典型薄膜太陽能電池 105 背部囊封物 110 基板 115 背部接觸層 120 吸收器層 147727.doc -41- 201042094 125 窗口層 130 頂部接觸層 135 頂部囊封物層 205 頂部囊封物層 210 頂部接觸層 215 CdS層 220 碲化編層 225 背部接觸層 230 囊封物層 235 玻璃 300 習用電沉積裝置 305 大池 310 電鍍溶液 315 連續基板 320 反電極 325 輥 400 流動歧管 405 歧管本體 410 反電極 415 電解液入口 420 已用電解液出口 425 連續片基板 500 電沉積系統/裝置 505 歧管本體 147727.doc -42- 201042094Figure 8A is an exploded view of an electrodeposition apparatus of Figure 8A. Figure 8B is a side cross-sectional view of the electrodeposition apparatus of Figure 8A. Figure 9 is a side cross-sectional view showing another electrodeposition apparatus in accordance with an embodiment of the present invention. Figure 10 illustrates a perspective view of another flow manifold in accordance with an embodiment of the present invention. Figure 11 continued to show a cross-sectional view of one of the electrodeposition systems including more than one electrodeposition crack in accordance with an embodiment of the present invention. Fig. 12 is a view showing a process flow relating to an electrodeposition method according to an embodiment of the present invention. [Main component symbol description] 100 typical thin film solar cell 105 back encapsulant 110 substrate 115 back contact layer 120 absorber layer 147727.doc -41- 201042094 125 window layer 130 top contact layer 135 top encapsulant layer 205 top encapsulation Object layer 210 top contact layer 215 CdS layer 220 ruthenium layer 225 back contact layer 230 encapsulant layer 235 glass 300 conventional electrodeposition apparatus 305 large pool 310 plating solution 315 continuous substrate 320 counter electrode 325 roller 400 flow manifold 405 Tube body 410 counter electrode 415 electrolyte inlet 420 used electrolyte outlet 425 continuous sheet substrate 500 electrodeposition system / device 505 manifold body 147727.doc -42- 201042094

510 反電極 515 電解液入口 520 電解液出口 525 基板 530 輥 535 材料 540 電解液 545 溢流通道 600 流動歧管 605 本體 610 反電極 615 電解液入口 620 電解液出口 625 基板 630 密封件 700 流動歧管 705 本體 710 反電極 715 電解液入口 720 密封件 725 孔口 800 實例性電沉積總成 801 本體 802 反電極 147727.doc -43 - 201042094 803 入口 804 出口 805 流動歧管 810 矩形密封件 815 連續基板 820 輥 900 電沉積總成 905 本體 910 反電極 915 密封件 920 基板 930 輥/孔口 935 孔口 1000 總成 1005 本體 1010 反電極 1015 電解液入口 1020 電解液出口 1025 密封件 1030 基板 1100 系統 1110 電沉積裝置 1120 電沉積裝置 1130 電沉積裝置 1140 基板 147727.doc -44-510 counter electrode 515 electrolyte inlet 520 electrolyte outlet 525 substrate 530 roller 535 material 540 electrolyte 545 overflow channel 600 flow manifold 605 body 610 counter electrode 615 electrolyte inlet 620 electrolyte outlet 625 substrate 630 seal 700 flow manifold 705 Body 710 Counter Electrode 715 Electrolyte Inlet 720 Seal 725 Port 800 Example Electrodeposition Assembly 801 Body 802 Counter Electrode 147727.doc -43 - 201042094 803 Inlet 804 Outlet 805 Flow Manifold 810 Rectangular Seal 815 Continuous Substrate 820 Roller 900 electrodeposition assembly 905 body 910 counter electrode 915 seal 920 substrate 930 roll / orifice 935 orifice 1000 assembly 1005 body 1010 counter electrode 1015 electrolyte inlet 1020 electrolyte outlet 1025 seal 1030 substrate 1100 system 1110 electrodeposition Device 1120 electrodeposition device 1130 electrodeposition device 1140 substrate 147727.doc -44-

Claims

201042094 七、申請專利範圍： 1· 一種電沉積裝置，其包括： (0 一移動總成，其用於在電沉積期間極接近於一反電極地定位一基板；及 (Π) 一流動歧管，其經組態以使一電解液在該基板與一 ' 反電極之間流動且連續地在該基板之電鍍表面與該反電極之間供應電解液； /、中該反電極係疋位於該流動歧管上或係該流動歧管之〇一組成組件。 2. 如請求項1之裝置，其中該移動總成經組態以移動一連、’’貝片型基板，該連續片型基板包括一導電材料及具有一導電塗層之一材料中之至少一者。 3. 如明求項2之裝置，其中該移動總成包括一驅動組件，該驅動組件經組態以在電沉積期間在大致不彎曲該基板之h开^/下將该連續片型基板移動過該流動歧管及反電極0 4 _如明求項3之裝置’其中該反電極經組態以當在電沉積期間該連續片型基板經過該反電極時大致跨過該連續片型基板之寬度。 5. 如請求項4之裝置’其中該反電極包括在電沉積期間大致平行於該基板之該表面定位之一大致平面表面。 6. 如請求項5之裝置’其中該反電極與該基板在電沉積期間相隔約2 mm與約10 mm之間。 7. 如請求項6之裝置’其中該流動歧管經組態以在該基板 147727.doc 201042094 一大致層流流動或一紊與該反電極之間產生該電解液之流流動。月求項7之裝置，其進一步包括一個或多個密封件，該等密封件經組態以引導電解液之該流動以便在電沉積期間最大化與該基板之接觸且最小化產生接觸該基板之電解液之該連續供應所需之電解液之量。 9.如明求項8之裝置，其進一步包括用於收集已用電解液之一個或多個溢流通道。如。月长項8之裝置，其中該一個或多個密封件經組態以在該流動歧管及該基板與該一個或多個密封件嚙合或極接近於該一個或多個密封件時在該基板與該流動歧管之間形成一室；該流動歧管進一步包括在電沉積期間各自含有於该室内之一電解液入口及一電解液出口。 11_如請求項1〇之裝置，其中該一個或多個密封件包括一週邊型密封件。 12. —種電沉積方法，其包括： (i) 在一基板之電鍍表面極接近於一反電極之同時使用向該基板供應一電解液之一連續供應之一流動歧管來使電解液在該基板與該反電極之間流動；及 (ii) 在該基板與該反電極之間施加一電鍍電位；其中該反電極經組態以大致跨過該基板之至少一個維度且係定位於該流動歧管上或係該流動歧管之—組成组件0 13.如請求項12之方法，其進一步包括在電沉積期間將該基 147727.doc -2- 201042094 板連續地移動過該反電極，其中該基板包括一連續片，该連續片包括一導電材料及具有一導電塗層之一材料中之至少一者。求項13之方法，其中該反電極與該基板在電沉積期間係定位為相隔約2 mm與約10 mm之間。 15. 如凊求項14之方法，其中使一電解液在該基板與該反電極之間流動包括在該基板與該反電極之間產生該電解液 ❹ 之大致層流流動或一奢流流動。 16. 如請求項15之方法，其進一步包括採用一個或多個密封件，該等密封件經組態以引導電解液之該流動以便在電沉積期間最大化與該基板之接觸且最小化產生接觸該基板之電解液之該連續供應所需之電解液之量。 17. 如清求項16之方法，其中該一個或多個密封件經組態以在該流動歧管及該基板與該一個或多個密封件嚙合時在該基板與該流動歧管之間形成一室；該流動歧管進一步〇包括經組態以向該室供應電解液之一電解液入口及經組態以在電沉積期間將已用電解液自該室排出之一電解液出Π。 18·如請求項17之方法，其中該一個或多個密封件包括一週邊型密封件。 19. 一種用於將一電鍍溶液遞送至一基板之表面之流動歧管’該流動歧管包括： (i) 一電解液入口 ’該電解液入口在以下位置之上游處； U7727.doc 201042094 (li)—反電極，該反電極安置於該流動歧管之一表面上；及 (iii)—電解液出口，該電解液出口在該反電極之下游；其中該流動歧管經組態以在該反電極與該基板之一表面之間自該電解液入口供應該電鍍溶液之一連續流動，以使得電鍍可在該基板之該表面上發生且然後經由該電解液出口排出。 2〇.如請求項19之流動歧管，其經組態以在該基板之該表面與該反電極之間產生該電鍍溶液之—大致層流流動或一棄流流動。 21.如請求項20之流動歧管，其進一步包括—個或多個密封件，該等密封件經組態以引導電鍍溶液之該流動以便在電沉積期間最大化與該基板之該表面之接觸且最小化產生接觸該基板之該電鍍溶液之該連續流動所需之電鍍溶液之量。 22_如請求項21之流動歧管，其進一步包括用於收集已用電解液之一個或多個溢流通道。 23. 如請求項21之流動歧管’其中該一個或多個密封件經组態以在該流動歧管及該基板與該一個或多個密封件嚙合時在該基板之該表面與該流動歧管之間形成一室。 24. 如請求項23之流動歧管，其中該—個或多個密封件包括一週邊型密封件。 147727.doc201042094 VII. Patent Application Range: 1. An electrodeposition apparatus comprising: (0 a mobile assembly for positioning a substrate in close proximity to a counter electrode during electrodeposition; and (Π) a flow manifold Configuring to cause an electrolyte to flow between the substrate and a 'counter electrode and continuously supply an electrolyte between the plated surface of the substrate and the counter electrode; /, the counter electrode system is located The flow manifold is or is a component of the flow manifold. 2. The apparatus of claim 1, wherein the mobile assembly is configured to move a continuous, ''seat type substrate, the continuous sheet substrate including The device of claim 2, wherein the mobile assembly comprises a drive assembly configured to be during electrodeposition Moving the continuous sheet substrate substantially through the flow manifold and the counter electrode 0 4 - the device of claim 3 wherein the counter electrode is configured to be during electrodeposition The continuous sheet substrate passes the reverse The width of the continuous sheet substrate is substantially across. 5. The device of claim 4 wherein the counter electrode comprises a substantially planar surface positioned substantially parallel to the surface of the substrate during electrodeposition. The device of item 5 wherein the counter electrode is spaced apart from the substrate by between about 2 mm and about 10 mm during electrodeposition. 7. The device of claim 6 wherein the flow manifold is configured to be on the substrate 147727. Doc 201042094 A substantially laminar flow or a flow of the electrolyte between the turret and the counter electrode. The device of clause 7 further comprising one or more seals configured to guide This flow of electrolyte maximizes contact with the substrate during electrodeposition and minimizes the amount of electrolyte required to produce the continuous supply of electrolyte contacting the substrate. 9. The device of claim 8, Further comprising one or more overflow channels for collecting used electrolytes, such as a device of month length item 8, wherein the one or more seals are configured to be in the flow manifold and the substrate and the one Or multiple Forming a chamber between the substrate and the flow manifold when the seal is engaged or in close proximity to the one or more seals; the flow manifold further comprising an electrolyte inlet each contained in the chamber during electrodeposition and An electrolyte outlet. The apparatus of claim 1 wherein the one or more seals comprise a perimeter seal. 12. An electrodeposition method comprising: (i) a plating surface on a substrate Very close to a counter electrode while continuously supplying one of the electrolytes to the substrate to supply a flow manifold to flow the electrolyte between the substrate and the counter electrode; and (ii) at the substrate and the counter Applying a plating potential between the electrodes; wherein the counter electrode is configured to span substantially at least one dimension of the substrate and is positioned on or associated with the flow manifold - component 0. The method of 12, further comprising continuously moving the substrate 147727.doc -2- 201042094 plate through the counter electrode during electrodeposition, wherein the substrate comprises a continuous sheet, the continuous sheet comprising a conductive material and There is at least one of a conductive coating of one material. The method of claim 13, wherein the counter electrode and the substrate are positioned between about 2 mm and about 10 mm apart during electrodeposition. 15. The method of claim 14, wherein flowing an electrolyte between the substrate and the counter electrode comprises generating a substantially laminar flow or a luxury flow between the substrate and the counter electrode . 16. The method of claim 15, further comprising employing one or more seals configured to direct the flow of the electrolyte to maximize contact with the substrate during electrodeposition and minimize generation The amount of electrolyte required for this continuous supply of electrolyte contacting the substrate. 17. The method of claim 16, wherein the one or more seals are configured to be between the substrate and the flow manifold when the flow manifold and the substrate are engaged with the one or more seals Forming a chamber; the flow manifold further includes an electrolyte inlet configured to supply an electrolyte to the chamber and configured to discharge an electrolyte from the chamber during electrodeposition . 18. The method of claim 17, wherein the one or more seals comprise a perimeter seal. 19. A flow manifold for delivering a plating solution to a surface of a substrate. The flow manifold comprises: (i) an electrolyte inlet 'the electrolyte inlet upstream of the following position; U7727.doc 201042094 ( Li) a counter electrode disposed on a surface of the flow manifold; and (iii) an electrolyte outlet downstream of the counter electrode; wherein the flow manifold is configured to The counter electrode and a surface of one of the substrates are continuously flowed from the electrolyte inlet to supply one of the plating solutions such that electroplating can occur on the surface of the substrate and then exit through the electrolyte outlet. 2. The flow manifold of claim 19, configured to generate a substantially laminar flow or a disposable flow between the surface of the substrate and the counter electrode. 21. The flow manifold of claim 20, further comprising one or more seals configured to direct the flow of the plating solution to maximize the surface of the substrate during electrodeposition Contacting and minimizing the amount of plating solution required to produce the continuous flow of the plating solution contacting the substrate. 22_ The flow manifold of claim 21, further comprising one or more overflow passages for collecting used electrolyte. 23. The flow manifold of claim 21 wherein the one or more seals are configured to flow on the surface of the substrate and the substrate when the flow manifold and the substrate are engaged with the one or more seals A chamber is formed between the manifolds. 24. The flow manifold of claim 23, wherein the one or more seals comprise a perimeter seal. 147727.doc