TW201527110A - Electrically conductive structure and method for producing same - Google Patents
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- TW201527110A TW201527110A TW103128604A TW103128604A TW201527110A TW 201527110 A TW201527110 A TW 201527110A TW 103128604 A TW103128604 A TW 103128604A TW 103128604 A TW103128604 A TW 103128604A TW 201527110 A TW201527110 A TW 201527110A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
- H10K30/53—Photovoltaic [PV] devices in the form of fibres or tubes, e.g. photovoltaic fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Description
本發明係關於導電構造物及其製造方法，特別是關於使用於有機薄膜太陽能電池之光電轉換元件及其製造方法。 The present invention relates to a conductive structure and a method of manufacturing the same, and more particularly to a photoelectric conversion element used in an organic thin film solar cell and a method of manufacturing the same.
近年，有機薄膜太陽能電池，由於與先前的矽或化合物半導體太陽能電池比較，製法簡便裝置成本低，期待作為未來的低成本太陽能電池。 In recent years, organic thin film solar cells are expected to be low-cost solar cells in the future due to the low cost of the simple method compared with the conventional germanium or compound semiconductor solar cells.
有機薄膜太陽能電池的基本的構造，係於一對電極之間，配置成為受體之有機導電層(n層)及成為施體之有機導電層(p層)的2層接合而成之光電轉換層。當光入射光電轉換層，則在光電轉換層生成電子電洞對之激子(exciton)。該激子在pn接合的界面擴散，藉由存在於界面的強電場分離成電子與電洞電荷。分離的電子與電洞，分別向包夾設置在光電轉換層的陰極(或電子傳輸層)及陽極(或電洞傳輸層)移動，而產生起電力。 The basic structure of an organic thin film solar cell is a photoelectric conversion between a pair of electrodes and a two-layer bonding of an organic conductive layer (n layer) of an acceptor and an organic conductive layer (p layer) serving as a donor. Floor. When light is incident on the photoelectric conversion layer, an exciton of an electron hole pair is generated in the photoelectric conversion layer. The excitons diffuse at the interface of the pn junction and are separated into electron and hole charges by a strong electric field existing at the interface. The separated electrons and holes are respectively moved to the cathode (or electron transport layer) and the anode (or the hole transport layer) of the photoelectric conversion layer to generate electric power.
在於有機薄膜太陽能電池，p型有機導電層，與n型有機導電層的pn接合的面積越大，發生電荷分離的機率越高，而光電轉換效率越大。擴大pn接合的面積的方法，有使一方的有機導電層(例如p層有機導電層)的表面形狀粗化的方法。 In the organic thin film solar cell, the p-type organic conductive layer, the larger the area of the pn junction with the n-type organic conductive layer, the higher the probability of charge separation and the higher the photoelectric conversion efficiency. The method of expanding the area of the pn junction has a method of roughening the surface shape of one organic conductive layer (for example, a p-layer organic conductive layer).
例如，於專利文獻1，記載有藉由使用具有既定的 黏度的下層形成用塗層液，產生塗佈不均，在表面形成具有凹凸之塗膜的方法。 For example, in Patent Document 1, it is described that it has a predetermined The coating liquid for forming the lower layer of the viscosity causes uneven coating and forms a coating film having irregularities on the surface.
此外，在於專利文獻2，記載有n模型有機導電層，係例如藉由粒子尺寸的大小形成晶域尺寸梯度之層所組成之有機薄膜太陽能電池。具體而言，專利文獻2的有機光電轉換裝置，係對於光電轉換層，藉由p型有機半導體-n型有機半導體的粒子(以下稱為「pn粒子」。)之粒徑的大小在晶域尺寸形成梯度之電荷分離促進區域，在光電轉換層的中心附近存在較多平均粒徑較小的pn粒子，增大顯現電荷分離功能的pn接合面積。此外，在於非專利文獻1，記載利用陽極氧化氧化鋁的細孔作為模製作有機導電層的凹凸的方法。此外，於非專利文獻2，記載關於對3-己基噻吩(3HT)照射X射線或電子線，於一部分形成聚(3-己基噻吩)(P3HT)。 Further, Patent Document 2 describes an n-type organic conductive layer, which is an organic thin film solar cell composed of, for example, a layer having a crystal size gradient formed by the size of a particle. Specifically, in the organic photoelectric conversion device of Patent Document 2, the size of the particle diameter of the particles of the p-type organic semiconductor-n-type organic semiconductor (hereinafter referred to as "pn particles") in the crystal field is in the crystal domain. The charge separation promoting region in which the size forms a gradient has a large number of pn particles having a small average particle diameter in the vicinity of the center of the photoelectric conversion layer, and the pn junction area exhibiting the charge separation function is increased. Further, Non-Patent Document 1 discloses a method of producing irregularities of an organic conductive layer by using pores of anodized alumina as a mold. Further, Non-Patent Document 2 discloses that X-ray or electron beam is irradiated to 3-hexylthiophene (3HT) to form poly(3-hexylthiophene) (P3HT) in part.
但是，上述表面粗化方法，基本上係藉由化學處理所實現者，故形成之粗面的形狀，依存於有機導電層表面的微觀的不均勻而為隨機，無法自由設計形成凹凸的地方、凹凸的大小及形狀。此外，凹凸的深度(高度)，亦依存於粗化的化學機構，故有一定的上限，於pn接合面積的增大化有所極限。 However, since the surface roughening method is basically realized by chemical treatment, the shape of the rough surface formed is random depending on the microscopic unevenness of the surface of the organic conductive layer, and it is not possible to freely design a place where the unevenness is formed. The size and shape of the bump. Further, since the depth (height) of the concavities and convexities also depends on the rough chemical mechanism, there is a certain upper limit, and the increase in the pn junction area is limited.
另一方面，有預先決定有機導電層的表面凹凸的深度(高度)或形成的地方，隔著既定的間隔，按照設計形成複數凸狀部的手法。例如，於專利文獻3，記載有一種光電轉換元件，其特徵在於：在於包含有機半導體層A、及聚合物半導體的光電轉換元件，與有機半導體層A相同極性的有機半導體B接於該有機半導體層A，而有機半導體B係平均寬高比為1~12 之單位構造。此外，專利文獻4，記載有使用用於作為電極構造體材料之硬化型樹脂組成物，形成具有矩形凹凸之有機導電層(p層)與有機導電層(n層)之手法。 On the other hand, there is a method of determining the depth (height) of the surface unevenness of the organic conductive layer or the place where it is formed, and forming a plurality of convex portions in accordance with a predetermined interval. For example, Patent Document 3 discloses a photoelectric conversion element including a photoelectric conversion element including an organic semiconductor layer A and a polymer semiconductor, and an organic semiconductor B having the same polarity as the organic semiconductor layer A is bonded to the organic semiconductor Layer A, and the average aspect ratio of organic semiconductor B is 1~12 Unit structure. Further, Patent Document 4 describes a method of forming an organic conductive layer (p layer) having a rectangular unevenness and an organic conductive layer (n layer) using a curable resin composition as an electrode structure material.
[專利文獻1]日本特開2007-073717號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-073717
[專利文獻2]日本特開2012-004299號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-004299
[專利文獻3]日本特開2011-100869號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-100869
[專利文獻4]日本特開2010-199101號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-199101
[非專利文獻1]ADVANCED FUNCTIONAL MATERIALS 2010, 20, 540-545 [Non-Patent Document 1] ADVANCED FUNCTIONAL MATERIALS 2010, 20, 540-545
[非專利文獻2]Journal of Macromolecular Science, Part A 2003, A40, 1357-1368 [Non-Patent Document 2] Journal of Macromolecular Science, Part A 2003, A40, 1357-1368
但是，記載於專利文獻3、4的凹凸形成的手法，提升載子傳輸效率(特別是電子的傳輸效率)及光起電力有所極限，而有進一步改善的餘地。 However, the methods of forming the concavities and convexities described in Patent Documents 3 and 4 have a limit for further improvement in improving carrier transmission efficiency (especially electron transmission efficiency) and light-emitting power.
本發明係在於隔著既定的間隔形成複數的導電性有機構造體的手法之中，以提升傳輸效率，例如可提升有機薄膜太陽能電池之光起電力之導電構造物、及其製造方法為目標。 The present invention is directed to a method of forming a plurality of conductive organic structures at predetermined intervals, thereby improving transmission efficiency, for example, a conductive structure capable of improving light-emitting power of an organic thin film solar cell, and a method for producing the same.
記載於專利文獻3、4之有機導電層的凸部，由於係矩形而存在著菱角，而電場容易在菱角的部分集中。在於有機導電層存在電場集中的部分，則會降低電子在於有機導電層內的傳輸效率，結果有降低光起電力的可能性。此外，由導電構造物的耐久性(長壽命)之面，亦推測很難說很好。 The convex portions of the organic conductive layers described in Patent Documents 3 and 4 have a rhombus because of a rectangular shape, and the electric field is likely to concentrate at a portion of the water chest. In the portion where the electric field concentrates in the organic conductive layer, the transmission efficiency of electrons in the organic conductive layer is lowered, and as a result, the possibility of light-up power is reduced. In addition, it is hard to say that the surface of the conductive structure (long life) is difficult to say.
在如此的假設之下，本發明者們所構成的導電構造物，具有：基材，及於該基材上，隔著既定的間隔形成之複數導電性有機構造體，該導電性有機構造體，係將上部作成曲面狀者。本發明，係在於隔著既定的間隔形成複數導電性有機構造體的手法中，將導電性有機構造體的上部作成曲面狀，故不容易發生電場集中，因此，可認為可改善電子的傳輸效率及導電構造物的耐久性(長壽命)。 Under the assumption of this, the conductive structure formed by the inventors of the present invention has a base material and a plurality of conductive organic structures formed on the base material at a predetermined interval, and the conductive organic structure , the upper part is made into a curved shape. According to the present invention, in the method of forming a plurality of conductive organic structures via a predetermined interval, the upper portion of the conductive organic structure is formed into a curved shape, so that electric field concentration is less likely to occur, and therefore, it is considered that electron transport efficiency can be improved. And durability (long life) of the conductive structure.
在於上述導電構造物，其中上述導電性有機構造體之9/10的高度的寬幅W1；及上述導電性有機構造體之1/10高度的寬幅W2，滿足下述(1)式為佳：W1/W2<1...(1)。 In the above-mentioned conductive structure, the width W 1 of the height of 9/10 of the conductive organic structure and the width W 2 of the height of 1/10 of the conductive organic structure satisfy the following formula (1) Better: W 1 /W 2 <1...(1).
在於上述導電構造物，其中上述導電性有機構造體之1/2高度的寬幅W3；及上述導電性有機構造體的高度H，滿足下述(2)式為佳：H/W3>2...(2)。 In the above-mentioned conductive structure, the width W 3 of the 1/2 height of the conductive organic structure and the height H of the conductive organic structure satisfy the following formula (2): H/W 3 > 2...(2).
在於上述導電構造物，其中上述基材係具有導電性之第1電極， 上述導電性有機構造體係第1導電型半導體，較佳的是進一步具有：第2導電型半導體層，其係覆蓋上述基材及上述導電性有機構造體而形成；及第2電極，其係形成在該第2導電型半導體層上。 In the above conductive structure, the substrate is a first electrode having conductivity, The first conductive semiconductor of the conductive organic structure system preferably further includes a second conductive semiconductor layer formed by covering the base material and the conductive organic structure, and a second electrode formed On the second conductive semiconductor layer.
在上述導電構造物，其中上述基材係第1導電型半導體層，上述導電性有機構造體係第1導電型半導體，較佳的是進一步具有：第1電極，其係形成於上述基材下形成的導電性；第2導電型半導體層，其係覆蓋上述基材及上述導電性有機構造體而形成；及第2電極，其係形成於該第2導電型半導體層上。 In the above-mentioned conductive structure, the substrate-based first conductive semiconductor layer, and the conductive organic structural system first conductive semiconductor preferably further includes a first electrode formed under the substrate Conductivity; a second conductive semiconductor layer formed by covering the substrate and the conductive organic structure; and a second electrode formed on the second conductive semiconductor layer.
在上述導電構造物，其中上述第2導電型半導體層，以導電性有機材料為佳。 In the above conductive structure, the second conductive semiconductor layer is preferably a conductive organic material.
上述導電構造物，可構成光電二極體(包含有機薄膜太陽能電池)或電晶體。 The conductive structure may constitute a photodiode (including an organic thin film solar cell) or a transistor.
在於上述導電構造物，其中可將上述第1電極及/或第2電極，以光穿透材料構成。 In the above-described conductive structure, the first electrode and/or the second electrode may be made of a light-transmitting material.
在於上述導電構造物，可良好地實施，以上述第1導電型之導電性有機構造體作為p型半導體，以上述第2導電型半導體層作為n型半導體之態樣。 In the above-described conductive structure, the first conductive type conductive organic structure is used as the p-type semiconductor, and the second conductive type semiconductor layer is used as the n-type semiconductor.
在於上述導電構造物，可良好地實施，於上述第1導電型之導電性有機構造體及上述第2導電型 之半導體層之間，形成導電度較該等低的半導體層之態樣。 The conductive structure can be satisfactorily implemented in the first conductive type conductive organic structure and the second conductive type Between the semiconductor layers, a semiconductor layer having a lower conductivity than the above is formed.
在於上述導電構造物，可良好地實施，將上述導電性有機構造體作成柱狀的態樣。 The conductive structure described above can be suitably carried out, and the conductive organic structure is formed into a columnar shape.
在於上述導電構造物，可良好地實施，將上述導電性有機構造體作成於一部分包含延在於與上述基材平行的方向的壁狀物。 In the above-mentioned conductive structure, the conductive organic structure can be favorably formed, and the conductive organic structure can be formed as a part of a wall extending in a direction parallel to the substrate.
在於上述導電構造物，其中上述導電性有機構造體，以p型導電性高分子構成為佳。 In the above-described conductive structure, the conductive organic structure is preferably a p-type conductive polymer.
在於上述導電構造物，其中形成上述p型導電性高分子之單體，以選自由噻吩、吡咯、苯胺、苯硫醚及其衍生物所組成之群之至少1種為佳。 In the above-mentioned conductive structure, the monomer forming the p-type conductive polymer is preferably at least one selected from the group consisting of thiophene, pyrrole, aniline, phenyl sulfide and derivatives thereof.
在於上述導電構造物，其中上述噻吩及其衍生物，以選自由3-己基噻吩、3-辛基噻吩及3,3-乙烯二氧噻吩所組成之群之至少一個為佳。 In the above conductive structure, the thiophene and the derivative thereof are preferably at least one selected from the group consisting of 3-hexylthiophene, 3-octylthiophene and 3,3-ethylenedioxythiophene.
在於上述導電構造物，其中上述p型導電性高分子，包含10聚物以上的聚合物為佳。 In the above-mentioned conductive structure, the p-type conductive polymer preferably contains a polymer of 10 or more.
在於上述導電構造物，其中上述p型導電性高分子，含有立體規則性構造為佳。 In the above-described conductive structure, the p-type conductive polymer preferably contains a stereoregular structure.
在於上述導電構造物，其中上述吡咯及其衍生物，以吡咯(PPy)為佳。 In the above conductive structure, the pyrrole and the derivative thereof are preferably pyrrole (PPy).
可解決上述課題之本發明之導電構造物之製造方法，包含：於基材上，形成包含單體之有機物層之步驟；及以該有機物層在大氣壓下的狀態，對該有機物層中的複數位置照射聚焦 放射線之步驟。 A method for producing an electrically conductive structure according to the present invention which can solve the above problems, comprising the steps of: forming an organic layer containing a monomer on a substrate; and using a plurality of the organic layer in the organic layer under atmospheric pressure Position illumination focus The step of radiation.
於上述方法，對包含單體之有機物層，例如藉由聚焦電子束的照射而單體的一部分聚合所形成之導電性有機構造體，上部成為曲面狀。此可推測，聚焦電子束的強度隨著遠離聚焦電子束的焦點(光點中心)而變低，此外，由於由光點中心散射的二次電子線的強度亦變低，而單體的聚合度隨著遠離光點中心非線形(急劇地)變低。 In the above method, the organic layer containing the monomer, for example, a conductive organic structure formed by polymerizing a part of the monomer by irradiation of a focused electron beam, has a curved upper portion. It can be inferred that the intensity of the focused electron beam becomes lower as it goes away from the focus (the center of the spot) of the focused electron beam, and further, since the intensity of the secondary electron beam scattered by the center of the spot becomes lower, the polymerization of the monomer The degree becomes non-linear (a sharply) as it moves away from the center of the spot.
再者，在於本發明之放射線，包含(1)α射線、重質子線、質子線之外的重荷電粒子線及β射線、(2)中子射線、(3)γ射線、特性X射線、(4)電子線、X射線。 Furthermore, the radiation of the present invention includes (1) an alpha ray, a heavy proton, a heavy charged particle beam other than the proton line, a beta ray, (2) a neutron ray, (3) a gamma ray, a characteristic X ray, (4) Electronic lines and X-rays.
上述導電構造物之製造方法，在於照射聚焦放射線之步驟，使上述基材上側為大氣壓，上述基材下側以真空狀態，聚焦放射線穿透上述基材由下側照射上述有機物層照射為佳。 In the method for producing a conductive structure, the step of irradiating the focused radiation is performed such that the upper side of the substrate is at atmospheric pressure, and the lower side of the substrate is in a vacuum state, and it is preferable that the focused radiation penetrates the substrate and the upper organic layer is irradiated with the lower side.
於上述導電構造物之製造方法，在於照射聚焦放射線之步驟，可將上述聚焦放射線的光點位置，對準上述基材與上述有機物層接觸的面。 In the method for producing the conductive structure, the step of irradiating the focused radiation may be performed to align the spot position of the focused radiation with the surface of the substrate in contact with the organic layer.
於上述導電構造物之製造方法，在於照射聚焦放射線之步驟，可良好地實施，將上述聚焦放射線的光點位置，對準較上述基材與上述有機物層接觸的面為上述有機物層側之態樣。 The method for producing the conductive structure described above is characterized in that the step of irradiating the focused radiation is performed satisfactorily, and the position of the spot of the focused radiation is aligned with the surface of the substrate and the organic layer to be the organic layer side. kind.
上述導電構造物之製造方法，係上述基材係具有導電性之第1電極，藉由對上述有機物層照射聚焦放射線所形成之導電性有 機構造體為第1導電型半導體層，較佳的是在於照射聚焦放射線之步驟之後，進一步包含：去除沒有照射聚焦放射線的部分之上述有機物層之步驟；於上述基材上及上述導電性有機構造體上，形成第2導電型半導體層之步驟；及於上述第2導電型半導體層上形成第2電極之步驟。 In the method for producing a conductive structure, the substrate is made of a conductive first electrode, and the conductivity formed by irradiating the organic layer with focused radiation is Preferably, the machine structure is a first conductive semiconductor layer, and after the step of irradiating the focused radiation, the method further includes: removing the organic layer that does not irradiate the focused radiation; and the conductive organic layer on the substrate a step of forming a second conductive semiconductor layer on the structure; and a step of forming a second electrode on the second conductive semiconductor layer.
上述導電構造物之製造方法，較佳的是進一步包含：於上述基材下形成具有導電性之第1電極之步驟；上述基材係第1導電型半導體層，藉由對上述有機物層照射聚焦放射線所形成之導電性有機構造體係第1導電型半導體，在於照射聚焦放射線之步驟之後，進一步包含：去除沒有照射聚焦放射線的部分之上述有機物層之步驟；於上述基材上及上述導電性有機構造體上，形成第2導電型半導體層之步驟；及於上述第2導電型半導體層上形成第2電極之步驟。 Preferably, the method for producing a conductive structure further includes a step of forming a first electrode having conductivity under the substrate, and the substrate is a first conductive semiconductor layer by irradiating the organic layer with a focus Conductive organic structure system formed by radiation, the first conductivity type semiconductor, after the step of irradiating the focused radiation, further includes a step of removing the organic layer in a portion where the focused radiation is not irradiated; and the conductive organic layer on the substrate a step of forming a second conductive semiconductor layer on the structure; and a step of forming a second electrode on the second conductive semiconductor layer.
於上述導電構造物之製造方法，可良好地使用光穿透材料作為上述基材。 In the method for producing a conductive structure described above, a light-transmitting material can be preferably used as the substrate.
於上述導電構造物之製造方法，可良好地使用金屬材料作為上述基材。 In the method for producing a conductive structure described above, a metal material can be preferably used as the substrate.
此外，本發明係關於導電性有機構造體之製造方法，其包含：於基材上形成包含單體之有機物層之步驟； 以該有機物層在大氣壓下的狀態，藉由對該有機物層中的複數位置照射聚焦放射線形成導電性有機構造體之步驟；去除沒有照射聚焦放射線的部分之上述有機物層之步驟；及去除上述基材之步驟。 Furthermore, the present invention relates to a method of producing a conductive organic structure, comprising: a step of forming an organic layer containing a monomer on a substrate; a step of forming a conductive organic structure by irradiating a plurality of positions in the organic layer with a focused radiation in a state of the organic layer under atmospheric pressure; a step of removing the organic layer not irradiating the portion of the focused radiation; and removing the base The steps of the material.
本發明之導電構造物，首先，係於基材上隔著既定的間隔構成複數導電性有機構造體，與隨機粗化有機導電層表面者不同，係可任意設計構築形成凹凸的地方、凹凸的大小或形狀。 In the conductive structure of the present invention, first, a plurality of conductive organic structures are formed on a substrate at a predetermined interval, and unlike the surface of the randomly roughened organic conductive layer, a place where irregularities or irregularities are formed can be arbitrarily designed and constructed. Size or shape.
此外，本發明的導電構造物，由於導電性有機構造體上部係曲面狀，故不容易在導電性有機構造體的上部發生電場集中，因此可提升電子的傳輸效率，例如可提升有機薄膜太陽能電池的光起電力。此外，由於不容易在導電性有機構造體上部發生電場集中，亦可貢獻於提升導電構造物的耐久性(壽命)。 Further, in the conductive structure of the present invention, since the upper portion of the conductive organic structure is curved, it is not easy to concentrate electric field in the upper portion of the conductive organic structure, so that electron transport efficiency can be improved, for example, an organic thin film solar cell can be improved. The light starts from electricity. Further, since it is not easy to cause electric field concentration in the upper portion of the conductive organic structure, it is also possible to contribute to improving the durability (life) of the conductive structure.
1‧‧‧陽極 1‧‧‧Anode
2‧‧‧第1導電型半導體層 2‧‧‧1st conductive semiconductor layer
3‧‧‧導電性有機構造體 3‧‧‧ Conductive organic structures
4‧‧‧第2導電型半導體層 4‧‧‧2nd conductive semiconductor layer
5‧‧‧陰極 5‧‧‧ cathode
6‧‧‧電壓計 6‧‧‧ voltmeter
7‧‧‧本質半導體層 7‧‧‧ Essential semiconductor layer
8‧‧‧有機物層 8‧‧‧Organic layer
9‧‧‧框架體 9‧‧‧Framework
10‧‧‧有機物層 10‧‧‧ organic layer
11‧‧‧Si3N4薄膜 11‧‧‧Si 3 N 4 film
12‧‧‧電子槍 12‧‧‧Electronic gun
13‧‧‧聚焦電子束 13‧‧‧ Focused electron beam
14‧‧‧電子透鏡 14‧‧‧Electronic lens
15‧‧‧腔體 15‧‧‧ cavity
16‧‧‧腔體 16‧‧‧ cavity
W1、W2‧‧‧寬幅 W 1 , W 2 ‧ ‧ wide
第1圖係在於本發明之實施形態1之有機薄膜太陽能電池之剖面圖。 Fig. 1 is a cross-sectional view showing an organic thin film solar cell according to Embodiment 1 of the present invention.
第2圖係在於本發明之實施形態2之有機薄膜太陽能電池之剖面圖。 Fig. 2 is a cross-sectional view showing an organic thin film solar cell according to a second embodiment of the present invention.
第3圖係在於本發明之實施形態3之有機薄膜太陽能電池之剖面圖。 Fig. 3 is a cross-sectional view showing an organic thin film solar cell according to a third embodiment of the present invention.
第4圖係在於本發明之實施形態1之有機薄膜太陽能電池 之步驟剖面圖。 Figure 4 is an organic thin film solar cell according to Embodiment 1 of the present invention. A step profile of the steps.
第5圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 Fig. 5 is a cross-sectional view showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
第6圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 Fig. 6 is a cross-sectional view showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
第7圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 Fig. 7 is a cross-sectional view showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
第8圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 Fig. 8 is a cross-sectional view showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
第9圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 Figure 9 is a cross-sectional view showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
第10圖係使用於實施例1~9之電子線照射系之剖面圖。 Fig. 10 is a cross-sectional view showing the electron beam irradiation system used in Examples 1 to 9.
第11圖係導電性有機構造體No.13之可見光顯微分光光譜譜。 Fig. 11 is a visible light microspectroscopy spectrum of the conductive organic structure No. 13.
第12圖係實施例2所得之導電性有機構造體之掃描式電子顯微鏡影像(以下稱為「SEM影像」。)。 Fig. 12 is a scanning electron microscope image (hereinafter referred to as "SEM image") of the conductive organic structure obtained in Example 2.
第13圖係實施例3所得之導電性有機構造體，傾斜40°觀察之SEM影像。 Fig. 13 is a SEM image of the conductive organic structure obtained in Example 3, observed at an inclination of 40°.
第14圖係實施例3所得之導電性有機構造體，由高度方向觀察之SEM影像。 Fig. 14 is a SEM image of the conductive organic structure obtained in Example 3 as viewed from the height direction.
第15圖係實施例3所得之導電性有機構造體，由寬幅方向觀察之SEM影像。 Fig. 15 is a view showing an SEM image of the conductive organic structure obtained in Example 3 as viewed in a wide direction.
第16圖係實施例5所得之導電性有機構造體，由高度方向觀察之SEM影像。 Fig. 16 is a SEM image of the conductive organic structure obtained in Example 5 as viewed from the height direction.
第17圖係實施例6所得之導電性有機構造體，傾斜35°觀察之SEM影像。 Fig. 17 is a SEM image of the conductive organic structure obtained in Example 6 observed at an inclination of 35°.
第18圖係實施例6所得之導電性有機構造體，由高度方向觀察之SEM影像。 Fig. 18 is a SEM image of the conductive organic structure obtained in Example 6 as viewed from the height direction.
第19圖係實施例7所得之導電性有機構造體，由高度方向觀察之SEM影像。 Fig. 19 is a view showing the SEM image of the conductive organic structure obtained in Example 7 as viewed in the height direction.
第20圖係實施例7所得之導電性有機構造體，由寬幅方向觀察之SEM影像 Figure 20 is a view showing the SEM image of the conductive organic structure obtained in Example 7 as viewed from the wide direction.
以下，關於本發明之實施形態，分成導電構造物之基本構成、導電構造物之構成材料、導電構造物之製造方法，說明。 Hereinafter, an embodiment of the present invention will be described as a basic configuration of a conductive structure, a constituent material of the conductive structure, and a method of manufacturing the conductive structure.
1.導電構造物之基本構成 1. The basic structure of conductive structures
(實施形態1) (Embodiment 1)
以下，使用第1圖說明本發明之實施形態1。 Hereinafter, the first embodiment of the present invention will be described using Fig. 1 .
第1圖係使用於本發明之實施形態1之導電構造物之例(有機薄膜太陽能電池)之剖面圖。在於第1圖，於第1電極之陽極1上，形成第1導電型半導體層2，於半導體層2上，隔著既定的間格複數形成第1導電型之導電性有機構造體3。導電性有機構造體3的排列形態，並無特別限定，例如，配置為柵格狀。 Fig. 1 is a cross-sectional view showing an example of an electrically conductive structure (organic thin film solar cell) used in the first embodiment of the present invention. In the first embodiment, the first conductive type semiconductor layer 2 is formed on the anode 1 of the first electrode, and the conductive organic structure 3 of the first conductivity type is formed on the semiconductor layer 2 via a predetermined number of spaces. The arrangement form of the conductive organic structure 3 is not particularly limited, and is, for example, arranged in a lattice shape.
導電性有機構造體3，係上部形成為曲面狀。再者，於半導體層2上及導電性有機構造體3上，形成與第1導電型相反導電型的第2導電型半導體層4。第1導電型為p型時，第2導電型為n型。於半導體層4形成第2電極之陰極5。 The conductive organic structure 3 is formed in a curved shape on the upper portion. Further, on the semiconductor layer 2 and the conductive organic structure 3, a second conductive type semiconductor layer 4 of a conductivity type opposite to that of the first conductivity type is formed. When the first conductivity type is a p-type, the second conductivity type is an n-type. A cathode 5 of a second electrode is formed on the semiconductor layer 4.
如第1圖所示，對有機薄膜太陽能電池照射光，則至少在於導電性有機構造體3及半導體層4生成電子電洞對的激子，該激子移向導電性有機構造體3與半導體層4的界面，藉由存在於界面的強電場，電荷分離成電子電洞。生成之電子係向陰極5，生成之電洞係向陽極1，分別移動。此係起電力的產生機構，在於第1圖之電壓計6，可感側按照光強度的電壓。 As shown in Fig. 1, when the organic thin film solar cell is irradiated with light, at least the conductive organic structure 3 and the semiconductor layer 4 generate excitons of electron hole pairs, and the excitons move to the conductive organic structure 3 and the semiconductor. At the interface of layer 4, the charge is separated into electron holes by a strong electric field existing at the interface. The generated electrons are directed to the cathode 5, and the generated holes are moved toward the anode 1, respectively. This is a mechanism for generating electric power, which is the voltmeter 6 of Fig. 1 and can sense the voltage according to the light intensity.
在於本發明，由於係於半導體層2上，隔著既定的間隔複數形成導電性有機構造體3，故與隨機粗化有機導電層表面者不同，可設計形成凹凸的地方、凹凸的大小或形狀。此外，本發明的導電構造物，由於係導電性有機構造體3的上部為曲面狀，故不容易在有機導電層內發生電場集中，因此可提升在於有機導電層內的電子傳輸效率，例如可提升有機薄膜太陽能電池之光起電力。 According to the present invention, since the conductive organic structure 3 is formed by a plurality of predetermined intervals, the surface of the organic conductive layer is randomly roughened, and the unevenness or the size or shape of the unevenness can be designed. . Further, in the conductive structure of the present invention, since the upper portion of the conductive organic structure 3 is curved, electric field concentration is unlikely to occur in the organic conductive layer, so that electron transport efficiency in the organic conductive layer can be improved, for example, Improve the light power of organic thin film solar cells.
在於本發明所謂「曲面狀」，係指具有曲面成分的表面，不只是球面、弧面，如圓柱的側面或圓錐的側面，根據方向包含如直線的表面亦包含。 The term "curved surface" as used in the present invention means a surface having a curved surface component, not only a spherical surface or a curved surface, such as a side surface of a cylinder or a side surface of a cone, and a surface including a straight line according to a direction is also included.
此外，本案發明所特定的頂部，與將柱狀物，以該柱狀物的軸方向垂直切斷的表面所形成的構造物不同，包含具有缺角的形狀。 Further, the top portion specified in the invention of the present invention is different from the structure formed by the surface of the column which is perpendicularly cut in the axial direction of the column, and includes a shape having a notch.
半導體層2，以增加第1導電型半導體層(半導體層2或導電性有機構造體3)與第2導電型半導體層4之接合面(以下有記載為「pn接合面」)的面積的觀點設置為佳，但並非本發明之必要構成要素。因此，於基材的陽極1上形成導電性有機構造體3之情形，則亦有在於作為基材之半導體層2上形成導電 性有機構造體3之情形。 In the semiconductor layer 2, the area of the joint surface of the first conductive semiconductor layer (the semiconductor layer 2 or the conductive organic structure 3) and the second conductive semiconductor layer 4 (hereinafter referred to as "pn junction surface") is increased. The setting is preferred, but is not an essential component of the present invention. Therefore, in the case where the conductive organic structure 3 is formed on the anode 1 of the substrate, the conductive layer 3 is formed on the semiconductor layer 2 as a substrate. The case of the sexual organic structure 3.
導電性有機構造體3，係上部叫下部細的形狀為佳。上部較下部粗的形狀，則電子或電洞的流動，有被導電性有機構造體3與半導體層4之間的pn接合面阻礙的可能性。因此，如第1圖所記載，在於導電性有機構造體3之9/10高度(上部)之寬幅W1，與導電性有機構造體3之1/10高度(下部)的寬幅W2，滿足下述(1)式為佳。 The conductive organic structure 3 is preferably a shape in which the upper portion is thin. In the shape in which the upper portion is thicker than the lower portion, the flow of electrons or holes may be hindered by the pn junction surface between the conductive organic structure 3 and the semiconductor layer 4. Therefore, as described in Fig. 1 , the width W 1 of the 9/10 height (upper portion) of the conductive organic structure 3 and the width W 2 of the 1/10 height (lower portion) of the conductive organic structure 3 are It is preferable to satisfy the following formula (1).
W1/W2<1...(1) W 1 /W 2 <1...(1)
此外，以增加pn接合的觀點，導電性有機構造體3的高度高為佳。 Further, from the viewpoint of increasing the pn junction, the height of the conductive organic structure 3 is preferably high.
因此，導電性有機構造體3之1/2高度(中部)的寬幅W3，與上述導電性有機構造體的高度H(全高)，滿足下述(2)式為佳。 Therefore, it is preferable that the width W 3 of the 1/2 height (middle portion) of the conductive organic structure 3 and the height H (all height) of the conductive organic structure satisfy the following formula (2).
H/W3>2...(2) H/W 3 >2...(2)
再者，導電性有機構造體3的高度或寬幅，(a)可根據導電性有機構造體3的剖面TEM影像實測，(b)將導電性有機構造體3以樹脂鑲埋研磨製作縱方向的剖面試料，藉由SEM觀察試料實測導電性有機構造體3的寬度，此外(c)亦可將導電性有機構造體3由傾斜方向觀察之斜角SEM影像按照傾斜角修正算出。 Further, the height or width of the conductive organic structure 3 can be measured by (a) the cross-sectional TEM image of the conductive organic structure 3, and (b) the conductive organic structure 3 can be polished by resin to form the vertical direction. In the cross-sectional sample, the width of the conductive organic structure 3 was measured by SEM observation, and (c) the oblique SEM image of the conductive organic structure 3 observed from the oblique direction was corrected by the inclination angle.
在於本發明之實施形態1，以使用導電構造物構成之有機薄膜太陽能電池之情形說明，但只要是包含導電性有機構造體3之形態，及可適用於各種半導體裝置。例如，二極體或電晶體等的整流元件、光電二極體、光電電晶體等的光電轉換元件，或亦可適用於該等元件之細微配線圖案等。 In the first embodiment of the present invention, an organic thin film solar cell comprising a conductive structure is used. However, the present invention can be applied to various semiconductor devices as long as it includes the conductive organic structure 3. For example, a photoelectric conversion element such as a rectifier element such as a diode or a transistor, a photodiode, or a photovoltaic transistor can be applied to a fine wiring pattern of the elements.
整流元件之具體例，可舉二極體(pn接合二極體、 蕭特基二極體、MOS二極體等)、電晶體(雙極電晶體、場效電晶體(FET)等)、閘流體，以及該等的複合元件(例如TTL等)等。 Specific examples of the rectifying element include a diode (pn junction diode, Schottky diodes, MOS diodes, etc.), transistors (bipolar transistors, field effect transistors (FETs), etc.), thyristors, and such composite components (such as TTL).
光電轉換元件的具體例，可舉電荷耦合元件(CCD)、光電增倍管，光耦合器等。將在於實施形態1之導電性有機構造體3，用於半導體裝置的哪個部位，並無特別限制，可使用於需要異質接合的部位。 Specific examples of the photoelectric conversion element include a charge coupled device (CCD), a photomultiplier tube, and an optical coupler. The conductive organic structure 3 of the first embodiment is used in any portion of the semiconductor device, and is not particularly limited, and can be used in a portion where heterojunction is required.
(實施形態2) (Embodiment 2)
以下，使用第2圖說明本發明之實施形態2。 Hereinafter, a second embodiment of the present invention will be described using Fig. 2 .
第2圖係使用本發明之實施形態2之導電構造物之例(有機薄膜太陽能電池)之剖面圖。在於第2圖，於第1導電型導電性有機構造體3與第2導電型半導體層4之間，形成導電度較該等低(電阻高)的本質半導體層7。如此之接合構成，係通常被稱為pin型接合，可使裝置高速，高效率動作者。再者，由於通常難以以單一組成的導電性有機物製作本質半導體層7，故亦可藉由p型有機半導體材料(施體)與n型有機半導體材料(受體)混合之層(亦稱為塊材異質接合層)而構成。 Fig. 2 is a cross-sectional view showing an example of an electrically conductive structure (organic thin film solar cell) according to a second embodiment of the present invention. In the second embodiment, an intrinsic semiconductor layer 7 having a lower conductivity (higher resistance) is formed between the first conductive type organic organic structure 3 and the second conductive type semiconductor layer 4. Such a joint configuration is generally referred to as a pin-type joint, which enables the apparatus to be high-speed and highly efficient. Furthermore, since it is generally difficult to form the intrinsic semiconductor layer 7 from a conductive organic substance having a single composition, it is also possible to mix a layer of a p-type organic semiconductor material (donor) with an n-type organic semiconductor material (receptor) (also referred to as a layer). It is composed of a bulk heterojunction layer).
(實施形態3) (Embodiment 3)
以下，使用第3圖說明本發明之實施形態3。 Hereinafter, a third embodiment of the present invention will be described using FIG.
在於本發明之實施形態1、2，以導電性有機構造體3係相互獨立排列之柱狀物之態樣說明，惟如第3圖所示，將導電性有機構造體3，作成於一部分包含延在於與基材(陽極1)平行的方向的壁狀物之態樣。藉由使導電性有機構造體3係於一部分包含壁狀物者，有可增加pn接合面積之情形。此外，藉由將聚焦電子束在基材的面內方向掃描，可高速製作導電性有機構造體3。 In the first and second embodiments of the present invention, the conductive organic structures 3 are arranged in a columnar shape in which the conductive organic structures 3 are arranged independently of each other. However, as shown in Fig. 3, the conductive organic structures 3 are partially included. The aspect of the wall extending in the direction parallel to the substrate (anode 1). When the conductive organic structure 3 is partially contained in a wall shape, the pn junction area can be increased. Further, the conductive organic structure 3 can be produced at a high speed by scanning the focused electron beam in the in-plane direction of the substrate.
2.導電構造物之構成材料 2. The constituent materials of the conductive structure
以下，說明使用於構成本發明之各構件之材料。 Hereinafter, materials used for constituting each member of the present invention will be described.
(1)陽極1、陰極5 (1) Anode 1, cathode 5
使用於陽極1、陰極5的材料，可使用例如，鋁或銅等的金屬材料。由於該等金屬材料導電性優良，可提升有機薄膜太陽能電池之能源轉換效率。再者，即使以鋁作為陽極1的材料時，確認可由陽極1下側的照射聚焦電子束，而聚焦電子束穿透陽極1，於導電構造物內形成導電性有機構造體3。 As the material used for the anode 1 and the cathode 5, for example, a metal material such as aluminum or copper can be used. Since the metal materials are excellent in electrical conductivity, the energy conversion efficiency of the organic thin film solar cells can be improved. Further, even when aluminum is used as the material of the anode 1, it is confirmed that the focused electron beam can be irradiated by the lower side of the anode 1, and the focused electron beam penetrates the anode 1, and the conductive organic structure 3 is formed in the conductive structure.
另一方面，將在於本發明之陽極1或陰極5之至少任意一方，以光穿透材料構成為佳。因為電極以光穿透材料構成，則可使光容易進出導電構造物內。此外，陽極1及陰極5的雙方，以光穿透材料構成，則由於光可貫通有機薄膜太陽能電池而穿透，故例如，將吸收波長不同的二種以上之有機薄膜太陽能電池層積複數(堆疊)，製作利用太陽光的複數波長之有機薄膜太陽能電池(串接型太陽能電池)。透明的導電性材料，可良好地使用例如，ITO(氧化銦錫)、IZO(氧化銦鋅)、ZnO(氧化鋅)所代表的透明氧化物導電膜。再者，以光穿透材料構成的陽極1或陰極5之光穿透率，以80%以上(對可見光線(波長380nm~780nm)之任意波長)為佳。 On the other hand, at least one of the anode 1 or the cathode 5 of the present invention is preferably formed of a light-transmitting material. Since the electrodes are constructed of a light-transmitting material, light can be easily introduced into and out of the conductive structure. Further, since both of the anode 1 and the cathode 5 are made of a light-transmitting material, since light can penetrate through the organic thin film solar cell, for example, two or more kinds of organic thin film solar cells having different absorption wavelengths are stacked ( Stacking), an organic thin film solar cell (series-type solar cell) using a plurality of wavelengths of sunlight. As the transparent conductive material, for example, a transparent oxide conductive film represented by ITO (indium tin oxide), IZO (indium zinc oxide), or ZnO (zinc oxide) can be preferably used. Further, the light transmittance of the anode 1 or the cathode 5 made of a light-transmitting material is preferably 80% or more (any wavelength of visible light (wavelength: 380 nm to 780 nm)).
(2)半導體層2 (2) Semiconductor layer 2
半導體層2，以p型半導體構成為佳。p型半導體，可使用p型有機半導體、p型無機半導體之任一。 The semiconductor layer 2 is preferably formed of a p-type semiconductor. As the p-type semiconductor, any of a p-type organic semiconductor and a p-type inorganic semiconductor can be used.
p型有機半導體，可舉具有以電子吸引性基取代的π電子共軛系化合物，可良好地使用以電子吸引性基取代的π電 子共軛系的p型導電性高分子。形成p型導電性高分子之單體，具體而言，可使用選自由噻吩、吡咯、呋喃、硒吩等的雜單環化合物；苯硫醚、異硫茚等的雜多環化合物；苯胺、酚等的苯衍生物；乙炔等的含有三鍵鍵結的化合物；薁等的芳香烴化合物，及由該等的衍生物所組成之群之至少1種。p型導電性高分子之單體，可單獨使用1種，亦可組合2種以上使用。 The p-type organic semiconductor may be a π-electron conjugated compound substituted with an electron attracting group, and a π-electrode substituted with an electron attracting group can be preferably used. Sub-conjugated p-type conductive polymer. The monomer forming the p-type conductive polymer may specifically be a heteropolycyclic compound selected from the group consisting of a heterocyclic compound such as thiophene, pyrrole, furan or selenophene; a heteropolycyclic compound such as phenyl sulfide or isothiopurine; and aniline. A benzene derivative such as phenol; a compound containing a triple bond such as acetylene; an aromatic hydrocarbon compound such as hydrazine; and at least one selected from the group consisting of such derivatives. The monomer of the p-type conductive polymer may be used alone or in combination of two or more.
p型無機半導體，可使用矽半導體等的先前習知之p型無機半導體。 As the p-type inorganic semiconductor, a conventional p-type inorganic semiconductor such as a germanium semiconductor can be used.
其中，半導體層2之p型半導體，由光穿透性的觀點以p型有機半導體為佳，以p型導電性高分子更佳，形成p型導電性高分子的單體，以雜單環化合物、雜多環化合物、苯衍生物為佳。p型導電性高分子之單體，以可電解聚合之單體為佳。此外，由更加提升半導體層2之光穿透性的觀點，形成p型導電性高分子之單體，以雜單環化合物為佳，以噻吩、吡咯更佳。半導體層2，亦可以與後述之導電性有機構造體3相同的材料構成。 Among them, the p-type semiconductor of the semiconductor layer 2 is preferably a p-type organic semiconductor from the viewpoint of light transmittance, and a p-type conductive polymer is more preferable, and a monomer of a p-type conductive polymer is formed, and a heterocyclic ring is formed. A compound, a heteropolycyclic compound or a benzene derivative is preferred. The monomer of the p-type conductive polymer is preferably an electropolymerizable monomer. Further, from the viewpoint of further improving the light transmittance of the semiconductor layer 2, a monomer of a p-type conductive polymer is formed, and a heteromonocyclic compound is preferred, and thiophene or pyrrole is more preferable. The semiconductor layer 2 may be made of the same material as the conductive organic structure 3 to be described later.
(3)導電性有機構造體3 (3) Conductive organic structure 3
導電性有機構造體3，以p型導電性高分子構成為佳。p型導電性高分子之單體，以可電解聚合之單體為佳，具體可良好地使用選自由噻吩、吡咯、呋喃等的雜單環化合物；苯硫醚等的雜多環化合物；苯胺等的芳香胺化合物；乙炔等的含有三鍵鍵結之化合物；薁等的芳香烴化合物；及其衍生物所組成之群之至少1種。形成p型導電性高分子之單體，可單獨使用1種，亦可組合2種以上使用，惟單獨使用1種為佳。 The conductive organic structure 3 is preferably composed of a p-type conductive polymer. The monomer of the p-type conductive polymer is preferably an electropolymerizable monomer, and specifically, a heteromonocyclic compound selected from the group consisting of thiophene, pyrrole, and furan; a heteropolycyclic compound such as phenyl sulfide; and aniline are preferably used. At least one of a group consisting of an aromatic amine compound, a compound containing a triple bond such as acetylene, an aromatic hydrocarbon compound such as hydrazine, and a derivative thereof. The monomer which forms the p-type conductive polymer may be used alone or in combination of two or more. It is preferred to use one type alone.
其中，形成p型導電性高分子之單體，以選自由噻吩、吡咯、苯胺、苯硫醚及其衍生物所組成之群之至少1種為佳。上述噻吩的衍生物，以3-己基噻吩、3-辛基噻吩、3,3-乙烯二氧噻吩為佳。此外，上述吡咯的衍生物，以吡咯本身為佳。再者，吡咯，可為非取代型及取代型之任一。 Among them, the monomer forming the p-type conductive polymer is preferably at least one selected from the group consisting of thiophene, pyrrole, aniline, phenyl sulfide, and derivatives thereof. The above derivatives of thiophene are preferably 3-hexylthiophene, 3-octylthiophene or 3,3-ethylenedioxythiophene. Further, the above pyrrole derivative is preferably pyrrole itself. Further, the pyrrole may be either an unsubstituted form or a substituted form.
此外，p型導電性高分子，以噻吩、吡咯、苯胺、苯硫醚、單獨使用該等的衍生物等的單體形成之p型導電性高分子之聚噻吩、聚吡咯、聚苯胺、聚苯硫醚及其衍生物為佳。聚噻吩的衍生物，以聚(3-己基噻吩)(P3HT)、聚(3-辛基噻吩)及聚(3,3-乙烯二氧噻吩)為佳，聚吡咯衍生物，以聚吡咯為佳。 Further, the p-type conductive polymer is a polythiophene, a polypyrrole, a polyaniline or a poly-p-type conductive polymer formed of a monomer such as thiophene, pyrrole, aniline, phenyl sulfide or a derivative thereof. Phenyl sulfide and its derivatives are preferred. Derivatives of polythiophenes, preferably poly(3-hexylthiophene) (P3HT), poly(3-octylthiophene) and poly(3,3-ethylenedioxythiophene), polypyrrole derivatives, polypyrrole good.
形成上述p型導電性高分子之單體(可電解聚合之單體)，係藉由後述之照射聚焦電子束之步驟聚合，形成p型導電性高分子。單體係形成n型導電性高分子之單體，則由即使照射聚焦電子束，亦不會形成導電性有機構造體之情形。再者，使用聚(3-己基噻吩)(P3HT)時之導電性有機構造體3之導電度，例如，於室溫(25℃)為10-10~10-7[S/cm]程度。 The monomer (electrolyzable polymerizable monomer) forming the p-type conductive polymer is polymerized by a step of irradiating a focused electron beam to be described later to form a p-type conductive polymer. When a single system forms a monomer of an n-type conductive polymer, a conductive organic structure is not formed even if a focused electron beam is irradiated. Further, the conductivity of the conductive organic structure 3 when poly(3-hexylthiophene) (P3HT) is used is, for example, about 10 -10 to 10 -7 [S/cm] at room temperature (25 ° C).
p型導電性高分子，以包含5聚物以上的聚合物為佳。以包含8聚物以上的聚合物更佳，進一步以包含10聚物以上的聚合物為佳。在此，所謂n聚物，係指n個單體聚合形成之聚合物。 The p-type conductive polymer is preferably a polymer containing 5 or more polymers. It is more preferable to use a polymer containing 8 or more polymers, and further preferably a polymer containing 10 or more polymers. Here, the n-polymer refers to a polymer formed by polymerizing n monomers.
p型導電性高分子之單體的鍵結數，可藉由例如，將p型導電性高分子浸漬於氯仿等的有機溶劑一定時間，將溶出成份以基質輔助雷射脫附游離-飛行時間質譜法(MALDI-TOF法)特定 。MALDI-TOF法，檢側可以上述有機溶劑溶析之成分之質量，可藉由除以單體的莫耳質量，算出單體的鍵結數。存在無法以浸漬有機溶劑溶析而殘存之n型導電性高分子時，可能存在較MALDI-TOF法所特定的單體的鍵結數更高的鍵結數之p型導電性高分子。 The number of bonds of the monomer of the p-type conductive polymer can be, for example, immersed in the organic solvent such as chloroform for a certain period of time, and the eluted component is desorbed by the matrix-assisted laser-free time-of-flight Mass spectrometry (MALDI-TOF method) specific . The MALDI-TOF method can detect the mass of the component which can be eluted by the above organic solvent, and the number of bonds of the monomer can be calculated by dividing the molar mass of the monomer. When there is an n-type conductive polymer which cannot be eluted by impregnation with an organic solvent, there may be a p-type conductive polymer having a higher number of bonds than the monomer specified by the MALDI-TOF method.
p型導電性高分子，以含有立體規則性構造為佳。包含立體規則性構造構造，則可提高p型導電性高分子的電荷傳輸性。所謂立體規則性構造，係指p型導電性高分子的取代基向一定方向排列存在的狀態。 The p-type conductive polymer preferably contains a stereoregular structure. When the three-dimensional regular structure is included, the charge transport property of the p-type conductive polymer can be improved. The stereoregular structure refers to a state in which the substituents of the p-type conductive polymer are arranged in a predetermined direction.
在於p型導電性高分子的立體規則性構造的存在，可例如，以可見光吸收光譜的最大吸收波長確認。例如已知，立體規則性構造的比例為90%以上的聚(3-己基噻吩)之情形，在於可見光吸收光譜於520~560nm附近顯示複數吸收波峰，另一方面，幾乎不具有立體規則性構造之立體無規則的聚(3-己基噻吩)之情形，在於可見光吸收光譜，於470nm附近顯示寬的吸收波峰，(Patel,R.J.,et al.,J.Polym.Sci.Pol.Phys.2011,49,1269-1275)。因此，測定所得聚(3-己基噻吩)之可見光吸收光譜時，只要吸收波峰超過470nm，則可說該聚(3-己基噻吩)，存在有立體規則性構造。 The existence of the stereoregular structure of the p-type conductive polymer can be confirmed, for example, by the maximum absorption wavelength of the visible light absorption spectrum. For example, it is known that the ratio of the stereoregular structure is 90% or more of poly(3-hexylthiophene), in which the visible light absorption spectrum exhibits a complex absorption peak near 520 to 560 nm, and on the other hand, it has almost no stereoregular structure. The case of the stereoregular poly(3-hexylthiophene) is a visible light absorption spectrum showing a broad absorption peak near 470 nm (Patel, RJ, et al., J. Polym. Sci. Pol. Phys. 2011, 49, 1269-1275). Therefore, when the visible light absorption spectrum of the obtained poly(3-hexylthiophene) is measured, the poly(3-hexylthiophene) can be said to have a stereoregular structure as long as the absorption peak exceeds 470 nm.
(4)半導體層4 (4) Semiconductor layer 4
半導體層4，以n型半導體形成為佳。n型半導體，可使用n型有機半導體、n型無機半導體之任一。 The semiconductor layer 4 is preferably formed of an n-type semiconductor. As the n-type semiconductor, either an n-type organic semiconductor or an n-type inorganic semiconductor can be used.
n型有機半導體，可舉具有富勒烯衍生物之化合物，可良好地使用具有富勒烯衍生物之n型導電性高分子。形成n 型導電性高分子的單體，可使用[6,6]-苯基-C61-酪酸甲酯(PCBM)、[6,6]-苯基-C61-酪酸正丁酯(PCBB)、[6,6]-苯基-C71-酪酸甲酯(PCBM)([70]PCBM)、二苯基-C62-雙(酪酸甲酯)(Bis[60]PCBM)。n型導電性高分子的單體，可以1種單獨使用，亦可組合2種以上使用。n型導電性高分子，使用PCBM為佳。 The n-type organic semiconductor may be a compound having a fullerene derivative, and an n-type conductive polymer having a fullerene derivative can be preferably used. Monomers forming the n-type conductive polymer, may be used [6,6] - phenyl -C 61 - casein acid methyl ester (PCBM), [6,6] - phenyl -C 61 - n-butyric acid ester (PCBB ), [6,6]-phenyl-C 71 -methyl butyrate (PCBM) ([70] PCBM), diphenyl-C 62 - bis (methyl butyrate) (Bis [60] PCBM). The monomer of the n-type conductive polymer may be used alone or in combination of two or more. For the n-type conductive polymer, it is preferable to use PCBM.
3.導電構造物之製造方法 3. Method for manufacturing conductive structure
接著，使用第4圖~第9圖說明製造第1圖所示本發明之實施形態1之導電構造物的方法。 Next, a method of manufacturing the electrically conductive structure of the first embodiment of the present invention shown in Fig. 1 will be described with reference to Figs. 4 to 9 .
第4圖~第9圖係在於本發明之實施形態1之有機薄膜太陽能電池之步驟剖面圖。 4 to 9 are cross-sectional views showing the steps of the organic thin film solar cell of the first embodiment of the present invention.
首先，如第4圖所示，於陽極1上，形成包含第1導電型單體之有機物層8，由陽極1之下側照射聚焦電子束。由於包含單體之有機物層8係液態，故藉由框體9，堵住有機物層8。 First, as shown in Fig. 4, an organic layer 8 containing a first conductivity type monomer is formed on the anode 1, and a focused electron beam is irradiated from the lower side of the anode 1. Since the organic layer 8 containing the monomer is in a liquid state, the organic layer 8 is blocked by the frame 9.
在於照射聚焦電子束時，使聚焦電子束的焦點(光點)設定對準在陽極1與有機物層8的境界附近，在陽極1與有機物層8的境界面內掃描聚焦電子束的焦點位置。電子線的焦點照到的部分的有機物層8發生聚合反應成為聚合物，形成如第5圖所示之第1導電型半導體層2。再者，半導體層2的形成方法，不限於以如此之聚焦電子束的掃描聚合，例如，亦有在陽極1上藉由旋轉塗佈法等預先形成的方法。 In order to illuminate the focused electron beam, the focus (light spot) of the focused electron beam is set to be aligned near the boundary between the anode 1 and the organic layer 8, and the focus position of the focused electron beam is scanned in the boundary between the anode 1 and the organic layer 8. The organic layer 8 in the portion where the focus of the electron beam is irradiated is polymerized to form a polymer, and the first conductive semiconductor layer 2 as shown in Fig. 5 is formed. Further, the method of forming the semiconductor layer 2 is not limited to the scanning polymerization using such a focused electron beam. For example, there is a method in which the anode 1 is formed in advance by a spin coating method or the like.
接著，如第5圖所示，使聚焦電子束的焦點(光點)設定對準在半導體層2與有機物層8的境界附近，以有機物層8在大氣壓下的狀態，對半導體層2與有機物層8的境界面內的1處，將聚焦電子束照射一定時間。藉此引起在於聚焦電子束的 焦點部分的有機物層8的聚合反應，如第6圖所示形成導電性有機構造體3。再者，對於形成之導電性有機構造體3隔著既定的間隔，於半導體層2上的其他處依序形成導電性有機構造體3。 Next, as shown in FIG. 5, the focus (light spot) of the focused electron beam is set in the vicinity of the boundary between the semiconductor layer 2 and the organic layer 8, and the semiconductor layer 2 and the organic substance are in a state where the organic layer 8 is under atmospheric pressure. At one location within the interface of layer 8, the focused electron beam is illuminated for a certain period of time. Thereby causing the focus of the electron beam The polymerization reaction of the organic layer 8 in the focus portion forms the conductive organic structure 3 as shown in Fig. 6. Further, the conductive organic structure 3 is formed on the semiconductor layer 2 at a predetermined interval with respect to the formed conductive organic structure 3.
再者，由於因半導體層2並非如上所述之本發明之必要條件，故亦可不製作半導體層2，以陽極1作為基材，於陽極1上形成直接導電性有機構造體3。 Further, since the semiconductor layer 2 is not required for the present invention as described above, the semiconductor layer 2 may not be formed, and the anode 1 may be used as a base material to form the direct conductive organic structure 3 on the anode 1.
以上述製造方法形成之導電性有機構造體3，上部成為曲面狀。此係，由於聚焦電子束的強度隨著遠離聚焦電子束的焦點(光點中心)而變低，此外，由光點中心散射的二次電子線的強度亦變低，故單體的聚合度亦隨著遠離光點中心而非線形(急劇)變低。 The conductive organic structure 3 formed by the above production method has a curved upper portion. In this system, since the intensity of the focused electron beam becomes lower as it goes away from the focus of the focused electron beam (the center of the spot), the intensity of the secondary electron beam scattered by the center of the spot also becomes lower, so the degree of polymerization of the monomer It also goes away from the center of the spot instead of the line (sharp).
本發明，由於係有機物層8在大氣壓下的狀態由陽極1下側對有機物層8照射聚焦電子束，故可於常溫促進聚合反應。對此，如將有機物層8放置於電子顯微鏡內部等的真空下之情形，為防止有機物層8的蒸散需要冷卻在極低溫，而難以提升有機物層8的聚合度。 In the present invention, since the organic material layer 8 is irradiated with the focused electron beam from the lower side of the anode 1 under the atmospheric pressure, the polymerization reaction can be promoted at normal temperature. On the other hand, when the organic layer 8 is placed under a vacuum inside the electron microscope or the like, it is necessary to cool at a very low temperature to prevent evapotranspiration of the organic layer 8, and it is difficult to increase the degree of polymerization of the organic layer 8.
關於將有機物層8置於大氣壓中，對有機物層8照射電子線的方法，使用市售的裝置，則可使用大氣壓SEM(掃描式電子顯微鏡)，環境TEM(穿透式電子顯微鏡)。 For the method of irradiating the organic layer 8 to atmospheric pressure and irradiating the organic layer 8 with an electron beam, a commercially available apparatus can be used, and an atmospheric pressure SEM (scanning electron microscope) or an environmental TEM (transmissive electron microscope) can be used.
在於對第5圖所示有機物層8照射聚焦放射線的步驟，雖亦可將聚焦放射線的焦點(光點)位置，對在基材的半導體層2與有機物層8之面，但將焦點位置對準較此面更有機物層8側(即有機物層8中)為佳。將焦點位置對準有機物層8之中，則聚焦電子束，係由對有機物層8的入射面向裡面(第5圖上方)進 一步朝向聚焦的形狀，故導電性有機構造體3，推測容易成為仿造聚焦電子束的形狀之尖細的形狀。 In the step of irradiating the organic material layer 8 shown in Fig. 5 with the focused radiation, the focus (light spot) of the focused radiation may be placed on the surface of the semiconductor layer 2 and the organic layer 8 of the substrate, but the focus position is It is preferable that the organic layer 8 side (that is, in the organic layer 8) is better than this side. By aligning the focus position with the organic layer 8, the electron beam is focused by the incident surface of the organic layer 8 (above the top of Fig. 5). Since the conductive organic structure 3 is oriented toward the focused shape in one step, it is presumed that it is a shape that is a sharp shape that mimics the shape of the focused electron beam.
接著，如第7圖所示，去除沒有照射聚焦電子束的部分的有機物層8之後，如第8圖所示，於導電性有機構造體3之基材之第1導電型半導體層2上，及導電性有機構造體3上，形成第2導電型半導體層4。最後，於第2導電型半導體層4上，形成陰極5，完成有機薄膜太陽能電池胞(第9圖)。 Next, as shown in FIG. 7, after removing the organic layer 8 which is not irradiated with the focused electron beam, as shown in FIG. 8, on the first conductive type semiconductor layer 2 of the substrate of the conductive organic structure 3, On the conductive organic structure 3, the second conductive semiconductor layer 4 is formed. Finally, a cathode 5 is formed on the second conductive semiconductor layer 4 to complete an organic thin film solar cell (Fig. 9).
此外，如第4圖所示，於第1導電型半導體層2上，形成包含單體之有機物層8，如第5圖所示，使有機物層8在大氣壓下的狀態，藉由對有機物層8中的複數位置照射聚焦電子束，形成如第6圖所示之導電性有機構造體，之後，藉由執行如第7圖所示，去除聚焦電子束沒有照射的部分的有機物層8之步驟，及未示於圖，去除基材之第1導電型半導體層2之步驟，可取得導電性有機構造體3本身。 Further, as shown in Fig. 4, an organic layer 8 containing a monomer is formed on the first conductive semiconductor layer 2, and as shown in Fig. 5, the organic layer 8 is in an atmospheric pressure state, and the organic layer is formed. The complex position in 8 illuminates the focused electron beam to form a conductive organic structure as shown in Fig. 6, and thereafter, the step of removing the organic layer 8 of the portion where the focused electron beam is not irradiated is performed by performing the method as shown in Fig. 7. The conductive organic structure 3 itself can be obtained by the step of removing the first conductive semiconductor layer 2 of the substrate, as shown in the figure.
本發明係主張以申請日為西元2013年8月26日之日本專利申請編號2013-175028為優先權。申請日為西元2013年8月26日之日本專利申請編號2013-175028之說明書全部內容以參考資料包含於本發明。 The present invention claims priority to Japanese Patent Application No. 2013-175028, filed on Aug. 26, 2013. The entire contents of the specification of Japanese Patent Application No. 2013-175028, filed on Aug. 26, 2013, are hereby incorporated by reference.
以下，舉實施例更具體說明本發明，惟本發明並非限定於下述實施照，當然可於適合前.後述趣旨的範圍適當加以變更實施，該等均包含於本發明之技術性範圍。 In the following, the present invention is not limited to the following embodiments, and the present invention is not limited thereto, and may be appropriately modified and implemented in the scope of the present invention, and these are all included in the technical scope of the present invention.
(IR顯微分光測定) (IR microspectrophotometry)
關於導電性有機構造體，作為光源使用SPring-8的BL43IR 的紅外放射光，以紅外顯微分光測定裝置(FT-IR感測器，使用Bruker公司製「VERTEX 70」，顯微鏡部使用Bruker公司製「HYPERION 2000」)測定吸光度。再者，光譜測定(IR顯微分光測定，可見光顯微分光測定)，係將導電性有機構造體製作在Si3N4膜上後，測定穿透導電性有機構造體與Si3N4膜的光，另外測定僅穿透Si3N4膜的光，作為參考扣除，得到光譜。 For the conductive organic structure, the infrared radiation of the BL43IR of SPring-8 is used as the light source, and the infrared microspectrophotometer (FT-IR sensor, "VERTEX 70" manufactured by Bruker) is used as the light source, and the microscope unit is manufactured by Bruker. "HYPERION 2000") measures the absorbance. Further, spectrometry (IR microspectrophotometry, visible light microspectrophotometry) was carried out by forming a conductive organic structure on a Si 3 N 4 film, and then measuring a conductive organic structure and a Si 3 N 4 film. The light was additionally measured for light that penetrated only the Si 3 N 4 film, and subtracted as a reference to obtain a spectrum.
(可見光顯微分光測定) (visible light microspectrophotometry)
關於導電性有機構造體，使用紫外可視光譜測定裝置(感測器，使用大塚電子公司製「MCPD-7000」，顯微鏡部使用尼康公司製「ECLIPSE80i」)測定吸光度。 For the conductive organic structure, the absorbance was measured using an ultraviolet visible spectrum measuring apparatus (sensor, "MCPD-7000" manufactured by Otsuka Electronics Co., Ltd., and "ECLIPSE80i" manufactured by Nikon Corporation).
(MALDI-TOF測定) (measured by MALDI-TOF)
將導電性有機構造體，浸漬於氯仿30分鐘，將溶析成分，使用MALDI-TOF型質量分析裝置(Bruker公司製「Autoflex-III」)測定質量分佈。 The conductive organic structure was immersed in chloroform for 30 minutes, and the mass fraction was measured, and the mass distribution was measured using a MALDI-TOF type mass spectrometer ("Autoflex-III" manufactured by Bruker).
(實施例1) (Example 1)
如第10圖所示，於底方具有厚度100nm的Si3N4薄膜11之試料保持用薄膜碟，加入3-己基噻吩(純度超過98%，東京化成工業株式會社)，形成深度1cm程度的有機物層10。之後，使用大氣壓掃描式電子顯微鏡(日本電子公司製「JASM-6200」)，以加速電壓10~30kV、照射電流1~500pA，一點照射聚焦電子束13，1~300秒。此時，腔體15、16內保持在真空。聚焦電子束13，係將由電子槍12所產生的電子線，藉由電子透鏡14調整，將焦點位置對準試料保持用薄膜碟之底面的Si3N4薄膜11的表面(3-己基噻吩側)。照射後，將剩餘的單體以乙腈清洗，得到 本發明之導電性有機構造體。將所得導電性有機構造體，測定IR顯微分光的結果，觀察到來自聚(3-己基噻吩)的波峰，可知單體之3-己基噻吩藉由聚焦電子束的照射而聚合。 As shown in Fig. 10, the sample holding film of the Si 3 N 4 film 11 having a thickness of 100 nm on the bottom side was added with 3-hexyl thiophene (purity exceeding 98%, Tokyo Chemical Industry Co., Ltd.) to a depth of about 1 cm. Organic layer 10. Thereafter, an atmospheric pressure scanning electron microscope ("JASM-6200" manufactured by JEOL Ltd.) was used, and the focused electron beam 13 was irradiated with an acceleration voltage of 10 to 30 kV and an irradiation current of 1 to 500 pA for 1 to 300 seconds. At this time, the inside of the cavities 15, 16 is kept under vacuum. The electron beam 13 is focused, and the electron beam generated by the electron gun 12 is adjusted by the electron lens 14 to align the focus position with the surface of the Si 3 N 4 film 11 on the bottom surface of the sample holding film disk (3-hexylthiophene side). . After the irradiation, the remaining monomer was washed with acetonitrile to obtain a conductive organic structure of the present invention. The obtained conductive organic structure was measured for IR microspectrophotometry, and a peak derived from poly(3-hexylthiophene) was observed, and it was found that the monomer 3-hexylthiophene was polymerized by irradiation of a focused electron beam.
此外，於照射300秒聚焦電子束的導電性有機構造體No.10、13，測定可見光吸收顯微分光測定的結果，最大吸收波長為488nm，確認包含立體規則性構造。將導電性有機構造體No.13的可見光顯微分光測定的結果示於第11圖。再者，MALDI-TOF測定的結果，以氯仿溶析的成分的分子量的最大值為1,750m/z，由3-己基噻吩的分子量(168.3g/mol)，可知至少生成10.4聚物的聚合物。此外，存在有即使浸漬於氯仿亦不溶析而殘存之導電性有機構造體，暗示可能生成鍵結數更多的聚合物。 Further, as a result of measurement of visible light absorption microspectrophotometry, the conductive organic structures No. 10 and 13 which irradiated the electron beam for 300 seconds were irradiated, and the maximum absorption wavelength was 488 nm, and it was confirmed that the stereoregular structure was included. The results of visible light microspectrophotometry of the conductive organic structure No. 13 are shown in Fig. 11. Further, as a result of MALDI-TOF measurement, the maximum molecular weight of the component eluted with chloroform was 1,750 m/z, and the molecular weight of 3-hexylthiophene (168.3 g/mol) revealed that at least a polymer of 10.4 was formed. . Further, there is a conductive organic structure which remains without being eluted even when immersed in chloroform, suggesting that a polymer having a larger number of bonds may be formed.
於第1表表示分別變更加速電壓、照射電流、照射時間時，將導電性有機構造體由上觀察時之寬幅。可知可藉由加速電壓、照射電流，照射時間，控制導電性有機構造體的寬幅。 In the first table, when the acceleration voltage, the irradiation current, and the irradiation time are changed, the width of the conductive organic structure when viewed from above is wide. It can be seen that the width of the conductive organic structure can be controlled by the acceleration voltage, the irradiation current, and the irradiation time.
(實施例2) (Example 2)
於第12圖表示以加速電壓30kV、照射電流63.5pA，一點照射1~10秒，取代以加速電壓10~30kV、照射電流1~500pA，一點照射1~300秒以外，進行與實施例1同樣的操作得到導電性有機構造體之掃描式電子顯微鏡(SEM)影像。藉由縮短照射時間，可知可進一步減少導電性有機構造體的寬度。於第2表表示製作各導電性有機構造體時之加速電壓、照射電流，照射時間，寬幅。 In the same manner as in the first embodiment, the acceleration voltage is 30 kV and the irradiation current is 63.5 pA, and the irradiation is performed for one to ten seconds at one point instead of the acceleration voltage of 10 to 30 kV and the irradiation current of 1 to 500 pA. The operation obtained a scanning electron microscope (SEM) image of the conductive organic structure. By shortening the irradiation time, it is understood that the width of the conductive organic structure can be further reduced. In the second table, the acceleration voltage, the irradiation current, the irradiation time, and the width when each conductive organic structure is produced are shown.
(實施例3) (Example 3)
以加速電壓30kV、照射電流63.5pA，一點照射2秒，取代以加速電壓10~30kV、照射電流1~500pA，一點照射1~300秒以外，進行與實施例1同樣的操作，得到導電性有機構造体No.20。將所得導電性有機構造體No.20，傾斜40°觀察之SEM影像示於第13圖，由高度方向觀察之SEM影像示於第14圖，由寬幅方向觀察的SEM影像示於第15圖。可知藉由對單體照射聚焦電子束，可得上部為曲面狀的導電性有機構造體。此外，在於No.20導電性有機構造體之9/10高度之寬幅(W1)為92nm，在於1/10高度的寬幅(W2)為144nm，1/2高度的寬幅(W3)為130nm，高度(H) 為305nm，再者算出，算出W1/W2之值，H/W3之值，係W1/W2=0.64(<1)、H/W3=2.35(>2)，得到滿足上述(1)式及(2)式者。 The same operation as in Example 1 was carried out to obtain a conductive organic compound at an acceleration voltage of 30 kV and an irradiation current of 63.5 pA for one second at a time instead of an acceleration voltage of 10 to 30 kV and an irradiation current of 1 to 500 pA. Structure No. 20. The obtained SEM image of the conductive organic structure No. 20 observed at an inclination of 40° is shown in FIG. 13 , the SEM image observed from the height direction is shown in FIG. 14 , and the SEM image viewed from the wide direction is shown in FIG. 15 . . It can be seen that by irradiating the focused electron beam to the monomer, a conductive organic structure having a curved upper portion can be obtained. Further, the width (W 1 ) of the 9/10 height of the No. 20 conductive organic structure is 92 nm, and the width (W 2 ) of the height of 1/10 is 144 nm, and the width of 1/2 is wide (W). 3 ) is 130 nm, height (H) is 305 nm, and further calculated, the value of W 1 /W 2 is calculated, and the value of H/W 3 is W 1 /W 2 =0.64 (<1), H/W 3 = 2.35 (>2), which satisfies the above formula (1) and (2).
(實施例4) (Example 4)
使用2質量%的吡咯(純度99%，關東化學株式會社製)水溶液取代3-己基噻吩，以加速電壓30kV、照射電流124pA，一點照射120秒之外，進行與實施例1同樣的操作製作導電性有機構造體No.21。所得導電性有機構造體No.21的尺寸(寬幅)為5μm。 In the same manner as in Example 1, except that 3-hexylthiophene was replaced with an aqueous solution of 2% by mass of pyrrole (purity: 99%, manufactured by Kanto Chemical Co., Ltd.) at an acceleration voltage of 30 kV and an irradiation current of 124 pA, the same operation as in Example 1 was carried out. Sexual organic structure No. 21. The size (width) of the obtained conductive organic structure No. 21 was 5 μm.
(實施例5) (Example 5)
使用加速電壓30kV、照射電流63.5pA，掃描速度8.2μm/秒掃描之外，進行與實施例1同樣的掃描得到導電性有機構造體No.22。導電性有機構造體No.22，於一部分內包含壁，對掃描方向垂直方向的尺寸(寬度)為1.3μm。 Conductive organic structure No. 22 was obtained by the same scanning as in Example 1 except that the acceleration voltage was 30 kV, the irradiation current was 63.5 pA, and the scanning speed was 8.2 μm/sec. The conductive organic structure No. 22 included a wall in a part thereof, and the dimension (width) in the direction perpendicular to the scanning direction was 1.3 μm.
(實施例6) (Example 6)
使用於厚度100nm的Si3N4薄膜11的上面(有機物層側)，濺鍍80nm厚的ITO的試料保持用薄膜碟，以加速電壓30kV、照射電流60pA，一點照射2秒之外，進行與實施例1同樣的操作，得到導電性有機構造體No.23。將所得導電性有機構造體No.23，由高度方向觀察之SEM影像示於第17、18圖所得導電性有機構造體No.23之尺寸(寬幅)為230nm。 The sample holding film disk of 80 nm thick ITO was sputtered on the upper surface of the Si 3 N 4 film 11 having a thickness of 100 nm (on the organic layer side), and an acceleration voltage of 30 kV and an irradiation current of 60 pA were irradiated for 2 seconds at a time. In the same manner as in Example 1, a conductive organic structure No. 23 was obtained. The SEM image of the obtained conductive organic structure No. 23 shown in the height direction was shown to be 230 nm in the size (width) of the conductive organic structure No. 23 obtained in Figs.
(實施例7) (Example 7)
使用吡咯取代3-己基噻吩，以加速電壓30kV、照射電流515pA，一點照射0.5秒之外，進行與實施例1同樣的操作得到導電性有機構造體No.24。將所得導電性有機構造體No.24，由寬幅方 向觀察的SEM影像示於第19圖。所得導電性有機構造體No.24，在9/10高度的寬幅(W1)為197nm，在1/10高度的寬幅(W2)為234nm，在1/2高度的寬幅(W3)為250nm，高度(H)為680nm。再者算出W1/W2之值、H/W3之值，係W1/W2=0.84、H/W3=2.7，得到滿足上述(1)式及(2)式者。 Conductive organic structure No. 24 was obtained by the same operation as in Example 1 except that the pyrrole was used in place of 3-hexylthiophene at an acceleration voltage of 30 kV and an irradiation current of 515 pA. The obtained conductive organic structure No. 24 is shown in Fig. 19 as an SEM image observed in a wide direction. The obtained conductive organic structure No. 24 had a width (W 1 ) of 197 nm at a height of 9/10, a width (W 2 ) at a height of 1/10 of 234 nm, and a width at a height of 1/2 (W). 3 ) is 250 nm and height (H) is 680 nm. Further, the values of W 1 /W 2 and the value of H/W 3 were calculated, and W 1 /W 2 = 0.84 and H/W 3 = 2.7 were obtained, and those satisfying the above formulas (1) and (2) were obtained.
(實施例8) (Example 8)
使用苯胺(純度99%，關東化學株式會社製)取代3-己基噻吩，以加速電壓30kV、照射電流515pA，一點照射1.2秒之外，進行與實施例1同樣的操作得到導電性有機構造體No.25。所得導電性有機構造體No.25，在9/10高度的寬幅(W1)為255nm，在1/10高度的寬幅(W2)為354nm，在1/2高度的寬幅(W3)為340nm，高度(H)為470nm。再者算出，W1/W2之值、H/W3之值，係W1/W2=0.72，得到滿足上述(1)式者。 The electroconductive organic structure No. was obtained by the same operation as in Example 1 except that 3-hexylthiophene was replaced with aniline (purity: 99%, manufactured by Kanto Chemical Co., Ltd.) at an acceleration voltage of 30 kV and an irradiation current of 515 pA. .25. The obtained conductive organic structure No. 25 had a width (W 1 ) of 255 nm at a height of 9/10, a width (W 2 ) at a height of 1/10 of 354 nm, and a width at a height of 1/2 (W). 3 ) is 340 nm and height (H) is 470 nm. Further, it is calculated that the value of W 1 /W 2 and the value of H/W 3 are W 1 /W 2 = 0.72, and those satisfying the above formula (1) are obtained.
(實施例9) (Example 9)
使照射時間為1.0秒之外，進行與實施例8同樣的操作，得到導電性有機構造體No.26。所得導電性有機構造體No.26，在9/10高度的寬幅(W1)為145nm1/在10高度的寬幅(W2)262nm1/在1/2高度的寬幅(W3)是210nm、高度(H)為320nm。再者算出，W1/W2之值，係W1/W2=0.55，得到滿足上述(1)式。 The conductive organic structure No. 26 was obtained in the same manner as in Example 8 except that the irradiation time was 1.0 second. The obtained conductive organic structure No. 26 had a wide width (W 1 ) at a height of 9/10 of 145 nm 1 / a width at a height of 10 (W 2 ) of 262 nm 1 / a width (W 3 ) at a height of 1/2 was 210 nm and height (H) were 320 nm. Also calculated, W 1 / W 2 of the value, based W 1 / W 2 = 0.55, obtained satisfies the above formula (1).
1‧‧‧陽極 1‧‧‧Anode
2‧‧‧第1導電型半導體層 2‧‧‧1st conductive semiconductor layer
3‧‧‧導電性有機構造體 3‧‧‧ Conductive organic structures
4‧‧‧第2導電型半導體層 4‧‧‧2nd conductive semiconductor layer
5‧‧‧陰極 5‧‧‧ cathode
6‧‧‧電壓計 6‧‧‧ voltmeter
W1、W2‧‧‧寬幅 W 1 , W 2 ‧ ‧ wide
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