TWI576447B - 沉積裝置及製造用於該沉積裝置之坩堝的方法 - Google Patents
沉積裝置及製造用於該沉積裝置之坩堝的方法 Download PDFInfo
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- TWI576447B TWI576447B TW101102796A TW101102796A TWI576447B TW I576447 B TWI576447 B TW I576447B TW 101102796 A TW101102796 A TW 101102796A TW 101102796 A TW101102796 A TW 101102796A TW I576447 B TWI576447 B TW I576447B
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- 230000008021 deposition Effects 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims description 35
- 238000000151 deposition Methods 0.000 claims description 34
- 239000011241 protective layer Substances 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004093 laser heating Methods 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Description
本發明係關於一種用於沉積薄層之沉積裝置及一種製造用於該沉積裝置之坩堝的方法。
該沉積裝置可用於例如在基板上沉積薄層太陽能電池之一些層或所有層。詳言之，可在基板上沉積銅膜、銦膜、鎵膜及硒膜以製造所謂CIGS太陽能電池。為此目的，將待沉積材料置於沉積裝置之坩堝中並加熱，同時使基板定位於與坩堝開口相對處。在坩堝內加熱材料引起材料蒸發且經由開口離開坩堝，從而覆蓋基板。
材料在坩堝內加熱時，可與坩堝自身材料反應，導致坩堝表面腐蝕且坩堝隨後隨時間退化。存在由鈦製成之坩堝用於蒸發材料之實例。該等坩堝揭示於例如US2008173241A及US2006096542A中。當在鈦坩堝內蒸發硒時，坩堝腐蝕及效率連續退化問題尤其嚴重。該等坩堝需要頻繁更換，導致製造成本高昂及頻繁停工。
在有些情況下，沉積器件中已使用由氧化鈦製成之坩堝。一種此類情況為使用如US2009061079A所述之由氧化鈦、氧化鉭、氧化鋯或氧化矽製成之坩堝來製造鋰離子電池組。整個坩堝使用該等惰性材料可減輕與沉積材料反應之問題。然而，該等瓷坩堝材料極脆且須非常小心地操作。當操作不當時或當曝露於急劇溫度變化時，其亦可能容易破裂，因此再次導致停工。
本發明之一個目標為提出一種用於沉積多種材料的可靠器件，其可使維護成本降低，從而在較長運行時間下提供穩固瀉流過程。
本發明藉由提供一種具有申請專利範圍第1項之特徵的沉積裝置及一種根據申請專利範圍第8項之特徵製造用於該裝置之坩堝的方法來達成此目標。本發明之有利具體實例為申請專利範圍附屬項之標的物。
本發明係基於由金屬製成之坩堝主體與保護層的組合優勢，保護層用於將該金屬材料與沉積材料分隔、從而保護坩堝免遭腐蝕。具有金屬主體時，坩堝具有對溫度變化之敏感性較小的優勢。此外，與完全由陶瓷材料製成之坩堝相比，製造金屬主體之坩堝可更便宜。
由於僅在坩堝內可接觸沉積材料，因此氧化鈦(TixOy)保護層僅覆蓋坩堝主體之部分或所有內表面即可足夠。然而，在其他具體實例中，保護層覆蓋整個坩堝主體可能較為有利，此舉甚至可能更容易達成。
除坩堝以外，沉積裝置需要置於坩堝內用於將沉積材料(例如硒)加熱至所需溫度以供沉積之加熱構件。雖然該加熱可藉由直接加熱沉積材料來進行，但首先加熱坩堝、使得沉積材料因此間接受熱可能較為有利。加熱構件因此可包含一或多個經配置而接觸或靠近坩堝之電阻加熱器。用於直接或間接加熱沉積/蒸發材料之其他加熱構件可包括感應加熱構件、雷射加熱構件、離子加熱構件或其他適合器件。
保護層覆蓋坩堝主體之步驟可剛好在新坩堝置入所用沉積裝置內之前進行。
可藉由諸如物理沉積或化學沉積之沉積法，例如將氧化鈦電鍍於金屬表面上而在坩堝主體表面上製造保護層。然而，在一個有利具體實例中，氧化鈦(TixOy)保護層為誘發氧化物層(induced oxide layer)。在此情況下，氧化鈦保護層係藉由將坩堝主體之內表面之該部分氧化而製成。為使此舉可行，坩堝之至少此表面部分必須由一定厚度的鈦基合金製成。換言之，坩堝主體可由頂層或頂層之一部分包含鈦基合金的層狀金屬結構製成。
若氧化鈦保護層為誘發氧化物層，則其可藉由在氧氣氛圍或富氧氛圍中，例如在熔爐內加熱坩堝主體來製成。
在一個有利具體實例中，坩堝主體由鈦基合金製成。其甚至可完全由鈦基合金製成，隨後用氧化鈦覆蓋或可將其表面氧化以建構氧化鈦保護層。
在本發明意義下，鈦基合金可為主要組成元素為鈦的任何金屬合金。換言之，鈦為在鈦基合金中比例最高的元素。該材料應含有足以形成覆蓋氧化鈦的鈦。該鈦基合金之鈦含量較佳為至少50重量%(wt%)。然而，鈦比例宜更高，諸如高於60 wt%、高於70 wt%、高於80 wt%、高於90 wt%或高於95 wt%。在本發明意義下，鈦基合金亦可為純鈦金屬或具有不同材料之污染物或雜質的鈦金屬。
在較佳具體實例中，坩堝主體之鈦基合金包含鈀。或者或另外，可向鈦基合金中添加其他元素以改良其物理或化學特性。
在有利具體實例中，坩堝主體由金屬片製成。可利用輥軋製程來製造金屬片。坩堝主體可由兩片或兩片以上接合在一起而構成。
覆蓋坩堝內表面之至少一部分之保護層較佳應具有至少50 nm、至少100 nm、至少150 nm、至少200 nm、至少300 nm或至少500 nm之厚度。保護層宜具有一定的最小厚度以保護坩堝主體之金屬。數奈米或數奈米以下之厚度對於此目的可能過低。另一方面，若保護層過厚，則其可能因氧化鈦之脆性結構而剝離。接著會使坩堝表面暴露且易於與蒸發材料反應。
在沉積裝置之一個較佳具體實例中，設置用於固持太陽能電池基板之構件以便將置於坩堝內之蒸發材料沉積於太陽能電池基板表面上。該沉積裝置可設計成例如用於沉積一個層或一些層供製造薄膜太陽能電池，較佳製造CIGS太陽能電池。特定言之，沉積裝置可設計成以硒塗佈基板。因此，固持構件宜允許鄰近坩堝開口置放實質上呈矩形之玻璃面板。
可藉由任何適合方法製造坩堝主體，接著用保護層完全或部分覆蓋。可用於製造坩堝主體金屬材料的一種較佳方法為輥軋製程，亦即熱軋或冷軋金屬。以此方式製成之金屬片接著可成形為坩堝主體。或者，可經由熔融金屬鑄造或經由機械加工金屬件獲得坩堝主體之全部或一部分。
以下描述中將參考所附示意圖更詳細地說明本發明具體實例之一些實施例。
圖1展示沉積裝置之示意圖，其包含由基板固持器5固持之基板4。基板4之表面41面向坩堝1，坩堝1填充有沉積材料3。加熱構件2圍繞坩堝1配置，其可加熱坩堝1且連續加熱沉積材料3，沉積材料3因此蒸發並凝結於待塗佈沉積材料3之基板表面41上。圖1中未展示包含坩堝1及基板固持器5之沉積裝置的其餘部分，例如其中置放坩堝1之真空室。
若坩堝1完全由金屬製成，則當加熱至足夠程度時沉積材料(蒸發材料)3可與坩堝2之內表面12反應。然而，根據本發明之坩堝1的內表面12至少部分由保護層13覆蓋。該坩堝1之有利具體實例示於圖2及圖3中。
雖然圖2中所示之坩堝1具有圓柱形側壁且可具有正方形、矩形、圓形或任何其他適當形狀，但圖3中所示之坩堝1具有錐形形狀。在兩種情況下，坩堝1包含坩堝主體11及保護層13，該保護層13覆蓋內表面12之至少一部分。在圖2及圖3中所示之具體實例中，坩堝1之整個內表面12由保護層13覆蓋。在其他較佳具體實例中，坩堝主體11可完全由保護層13覆蓋。
圖2及圖3中所示之坩堝各自具備用於加熱蒸發材料(圖2及圖3中未圖示)以促進其蒸發至基板4上的加熱構件2。雖然其在圖中示意性展示為電阻加熱器，但加熱構件2可包含用於將能量轉移至坩堝1內之蒸發材料3上以使蒸發材料3之顆粒逸出坩堝1並沉積於基板表面41上的任何種類之加熱器件。該等器件之實例包括感應加熱構件、雷射加熱構件、離子加熱構件及其類似物。
圖4a)、圖4b)及圖4c)示意性地說明根據一個較佳具體實例製造具有保護層12之坩堝1的方法。為執行此程序，提供具有由金屬製成之坩堝主體11的坩堝1，如圖4a)中所示。坩堝主體11可由例如藉由輥軋製程獲得之金屬片製成。用於此製程之坩堝主體12較佳由鈦基合金製成。
在隨後步驟中，如圖4b)中所示，將坩堝主體12置於熔爐6中以便加熱。藉由在氧氣氛圍中加熱坩堝，將坩堝之整個表面或在受限制曝露於氧氣的情況下將坩堝之部分表面氧化，從而形成圖4c)中示意性所示的保護層13。另外可藉由諸如物理沉積或化學沉積之沉積方法強化保護層13。或者，可利用該等方法製造整個保護層13。
1．．．坩堝
2．．．加熱構件
3‧‧‧蒸發材料(沉積材料)
4‧‧‧基板
5‧‧‧基板固持器
6‧‧‧熔爐
11‧‧‧基板主體
12‧‧‧內表面
13‧‧‧保護層
41‧‧‧基板表面
圖1展示用於自坩堝將材料沉積於基板上的裝置；
圖2及圖3展示根據本發明之沉積裝置之坩堝的不同具體實例；及
圖4a)至圖4c)說明用於製造根據本發明之一個具體實例之坩堝的方法。
1．．．坩堝
2．．．加熱構件
11．．．基板主體
12．．．內表面
13．．．保護層
Claims (7)
- 一種沉積裝置，其包含坩堝(1)及配置用於加熱該坩堝(1)內之蒸發材料(3)的加熱構件(2)，其中該坩堝(1)包含金屬主體(11)及包含氧化鈦(TixOy)之保護層(13)，該保護層(13)覆蓋該金屬主體(11)之內表面(12)的至少一部分，其中該保護層具有至少50nm之厚度，且其中該保護層(13)之氧化鈦(TixOy)為誘發氧化物層。
- 如申請專利範圍第1項之沉積裝置，其特徵在於該坩堝之主體係由鈦基合金製成。
- 如申請專利範圍第2項之沉積裝置，其特徵在於該鈦基合金包含鈀。
- 如申請專利範圍第1項之沉積裝置，其特徵在於該坩堝之該主體係由金屬片製成。
- 如申請專利範圍第1項之沉積裝置，其特徵在於設置用於固持太陽能電池基板之構件以將置於該坩堝(1)內之蒸發材料(3)沉積於該太陽能電池基板之表面上。
- 一種製造用於沉積裝置之坩堝的方法，該方法包含以下步驟：提供由金屬材料製成之坩堝主體；及藉由包含氧化鈦(TixOy)之保護層覆蓋該金屬主體之內表面之至少一部分，其中該保護層具有至少50nm之厚度，且其中該氧化鈦保護層係藉由氧化坩堝主體之內表面之該部分來製成。
- 如申請專利範圍第6項之方法，其特徵在於用於坩堝之主體的該金屬材料係在輥軋製程中製成。
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| KR101582672B1 (ko) * | 2013-12-17 | 2016-01-05 | (주)알파플러스 | 증발용 도가니와 이를 포함하는 진공 증발원 및 진공 증착 장치 |
| KR20190029589A (ko) * | 2016-06-17 | 2019-03-20 | 도카로 가부시키가이샤 | 발열부재 |
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| EP2670877A1 (de) | 2013-12-11 |
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| TW201233831A (en) | 2012-08-16 |
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