JP3223738U - Glass substrate for solar cell - Google Patents
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- JP3223738U JP3223738U JP2019002172U JP2019002172U JP3223738U JP 3223738 U JP3223738 U JP 3223738U JP 2019002172 U JP2019002172 U JP 2019002172U JP 2019002172 U JP2019002172 U JP 2019002172U JP 3223738 U JP3223738 U JP 3223738U
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- 239000011521 glass Substances 0.000 title claims abstract description 199
- 239000000758 substrate Substances 0.000 title claims abstract description 171
- 238000009434 installation Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 97
- 238000012545 processing Methods 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000011810 insulating material Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims 1
- 230000008859 change Effects 0.000 description 54
- 238000000034 method Methods 0.000 description 25
- 238000010583 slow cooling Methods 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 11
- 229910001887 tin oxide Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- -1 tin tetrachloride Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 229960000956 coumarin Drugs 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 239000005357 flat glass Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
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- 229960002477 riboflavin Drugs 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
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- 239000005368 silicate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
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- Photovoltaic Devices (AREA)
Abstract
【課題】反りを抑制することが可能な太陽電池用ガラス基板を提供する。【解決手段】太陽電池用ガラス基板は、厚さが２ｍｍ以下のガラス板１と、ガラス板１上に形成された導電膜２と、導電膜２上に形成された機能膜３と、を備え、導電膜２の膜厚が０．２〜１．０μｍであり、導電膜２の膜抵抗値が８〜２５Ω／□である。太陽電池用ガラス基板を、ガラス板１が設置面と対向するように、当該設置面上に配置したとき、機能膜２の表面のうち、設置面との距離が最大となる位置における距離と、設置面との距離が最小となる位置における距離との差を反り変形量と規定し、反り変形量が、０．１〜１．０ｍｍである。【選択図】図１A glass substrate for a solar cell capable of suppressing warpage is provided. A glass substrate for a solar cell includes a glass plate 1 having a thickness of 2 mm or less, a conductive film 2 formed on the glass plate 1, and a functional film 3 formed on the conductive film 2. The film thickness of the conductive film 2 is 0.2 to 1.0 μm, and the film resistance value of the conductive film 2 is 8 to 25 Ω / □. When the glass substrate for solar cell is arranged on the installation surface such that the glass plate 1 faces the installation surface, among the surfaces of the functional film 2, the distance at the position where the distance from the installation surface is maximum, The difference from the distance at the position where the distance from the installation surface is minimum is defined as the warpage deformation amount, and the warpage deformation amount is 0.1 to 1.0 mm. [Selection] Figure 1
Description
本考案は、太陽電池用ガラス基板に関する。 The present invention relates to a glass substrate for a solar cell.
特許文献１には、太陽電池に用いられるガラス基板が開示されている。このガラス基板は、ガラス板の表面に導電膜が形成されたものであり、この導電膜上には、さらに機能膜が積層され、色素増感型太陽電池用、ＣｄＴｅ太陽電池用等の種々のガラス基板が作製される。 Patent Document 1 discloses a glass substrate used for a solar cell. In this glass substrate, a conductive film is formed on the surface of a glass plate, and a functional film is further laminated on the conductive film, and various kinds of films such as for dye-sensitized solar cells and CdTe solar cells are used. A glass substrate is produced.
ところで、上記のような機能膜が積層されるときには、ガラス基板に焼成等の熱処理を行うが、この熱処理によってガラス基板に反りが生じることがある。これは、ガラス板と導電膜との線膨張係数が相違するためである。したがって、このような反りを低減できる太陽電池用ガラス基板が要望されていた。本考案は、上記問題を解決するためになされたものであり、反りを抑制することが可能な太陽電池用ガラス基板を提供することを目的とする。 By the way, when the functional films as described above are laminated, a heat treatment such as baking is performed on the glass substrate, and the glass substrate may be warped by this heat treatment. This is because the linear expansion coefficients of the glass plate and the conductive film are different. Accordingly, there has been a demand for a glass substrate for a solar cell that can reduce such warpage. This invention is made | formed in order to solve the said problem, and it aims at providing the glass substrate for solar cells which can suppress curvature.
項１．厚さが２ｍｍ以下のガラス板と、
前記ガラス板上に形成された導電膜と、
前記導電膜上に形成された機能膜と、
を備えている、太陽電池用ガラス基板。
Item 1. A glass plate having a thickness of 2 mm or less;
A conductive film formed on the glass plate;
A functional film formed on the conductive film;
A glass substrate for solar cells.
項２．前記太陽電池用ガラス基板を、前記ガラス板が設置面と対向するように、当該設置面上に配置したとき、前記機能膜の表面のうち、前記設置面との距離が最大となる位置における前記距離と、前記設置面との距離が最小となる位置における前記距離との差を反り変形量と規定し、
前記反り変形量が、０．１〜１．０ｍｍである、項１に記載の太陽電池用ガラス基板。
Item 2. When the solar cell glass substrate is disposed on the installation surface such that the glass plate faces the installation surface, among the surfaces of the functional film, the position at the position where the distance from the installation surface is maximum. The difference between the distance and the distance at the position where the distance from the installation surface is minimum is defined as the amount of warpage deformation,
Item 2. The glass substrate for a solar cell according to Item 1, wherein the warp deformation amount is 0.1 to 1.0 mm.
項３．前記反り変形量が、０．１〜０．５ｍｍである、項２に記載の太陽電池用ガラス基板。 Item 3. Item 3. The solar cell glass substrate according to Item 2, wherein the warp deformation amount is 0.1 to 0.5 mm.
項４．前記反り変形量が、０．１〜０．３ｍｍである、項２に記載の太陽電池用ガラス基板。 Item 4. Item 3. The solar cell glass substrate according to Item 2, wherein the warp deformation amount is 0.1 to 0.3 mm.
項５．前記導電膜の膜抵抗値が、８〜２５Ω／□である、項１から４のいずれかに記載の太陽電池用ガラス基板。 Item 5. Item 5. The solar cell glass substrate according to any one of Items 1 to 4, wherein the conductive film has a film resistance value of 8 to 25Ω / □.
項６．前記導電膜の膜厚が、０．２〜１．０μｍである、項１から５のいずれかに記載の太陽電池用ガラス基板。 Item 6. Item 6. The solar cell glass substrate according to any one of Items 1 to 5, wherein the conductive film has a thickness of 0.2 to 1.0 μm.
項７．前記導電膜の膜厚が、０．２〜０．６μｍである、項１から５のいずれかに記載の太陽電池用ガラス基板。 Item 7. Item 6. The solar cell glass substrate according to any one of Items 1 to 5, wherein the conductive film has a thickness of 0.2 to 0.6 μm.
項８．前記導電膜の膜厚が、０．２〜０．４μｍである、項１から５のいずれかに記載の太陽電池用ガラス基板。 Item 8. Item 6. The solar cell glass substrate according to any one of Items 1 to 5, wherein the conductive film has a thickness of 0.2 to 0.4 μm.
項９．前記ガラス板の厚みが、１．６ｍｍ以下である、項１から８のいずれかに記載の太陽電池用ガラス基板。 Item 9. Item 9. The solar cell glass substrate according to any one of Items 1 to 8, wherein the glass plate has a thickness of 1.6 mm or less.
項１０．前記ガラス板の厚みが、１．１ｍｍ以下である、項１から８のいずれかに記載の太陽電池用ガラス基板。 Item 10. Item 9. The solar cell glass substrate according to any one of Items 1 to 8, wherein the glass plate has a thickness of 1.1 mm or less.
項１１．前記ガラス板の厚みが、０．８ｍｍ以下である、項１から８のいずれかに記載の太陽電池用ガラス基板。 Item 11. Item 9. The solar cell glass substrate according to any one of Items 1 to 8, wherein the glass plate has a thickness of 0.8 mm or less.
項１２．前記機能膜が、ＣｄＴｅ層を含有する、項１から１１のいずれかに記載の太陽電池用ガラス基板。 Item 12. Item 12. The solar cell glass substrate according to any one of Items 1 to 11, wherein the functional film contains a CdTe layer.
項１３．前記機能膜が、色素を担持した多孔質半導体層である、項１から１１のいずれかに記載の太陽電池用ガラス基板。 Item 13. Item 12. The solar cell glass substrate according to any one of Items 1 to 11, wherein the functional film is a porous semiconductor layer carrying a dye.
項１４．前記機能膜の膜厚が、１〜１０μｍである、項１３に記載の太陽電池用ガラス基板。 Item 14. Item 14. The solar cell glass substrate according to Item 13, wherein the functional film has a thickness of 1 to 10 μm.
項１５．前記ガラス板に前記導電膜が積層された後、前記機能膜が、加熱温度４８０〜５８０℃とする熱処理条件により積層される、項１から１４のいずれかに記載の太陽電池用ガラス基板。 Item 15. Item 15. The glass substrate for a solar cell according to any one of Items 1 to 14, wherein after the conductive film is stacked on the glass plate, the functional film is stacked under a heat treatment condition of a heating temperature of 480 to 580 ° C.
項１６．前記ガラス板に前記導電膜が積層された後、前記機能膜が、加熱時間１０〜２００分とする熱処理条件により積層される、項１から１５のいずれかに記載の太陽電池用ガラス基板。 Item 16. Item 16. The solar cell glass substrate according to any one of Items 1 to 15, wherein the functional film is laminated under a heat treatment condition of a heating time of 10 to 200 minutes after the conductive film is laminated on the glass plate.
項１７．前記熱処理条件として、昇温速度が３℃／分以上である、項１５または１６に記載の太陽電池用ガラス基板。 Item 17. Item 17. The solar cell glass substrate according to Item 15 or 16, wherein the heat treatment condition is a temperature rising rate of 3 ° C./min or more.
項１８．前記熱処理条件として、昇温速度が１００℃／分以上である、項１５または１６に記載の太陽電池用ガラス基板。 Item 18. Item 17. The solar cell glass substrate according to Item 15 or 16, wherein the heat treatment condition is a rate of temperature increase of 100 ° C./min or more.
項１９．前記熱処理条件として、昇温速度が１５０℃／分以上である、項１５または１６に記載の太陽電池用ガラス基板。 Item 19. Item 17. The solar cell glass substrate according to Item 15 or 16, wherein the heat treatment condition is a rate of temperature increase of 150 ° C./min or more.
項２０．前記機能膜を上側に向け、前記ガラス板の周縁の少なくとも一部を支持した状態で、前記熱処理を行う、項１５から１９のいずれかに記載の太陽電池用ガラス基板。 Item 20. Item 20. The solar cell glass substrate according to any one of Items 15 to 19, wherein the heat treatment is performed in a state in which the functional film is directed upward and at least a part of a peripheral edge of the glass plate is supported.
項２１．前記太陽電池用ガラス基板の周縁に保温材を配置した状態で、前記熱処理後の徐冷を行う、項１５から２０のいずれかに記載の太陽電池用ガラス基板。 Item 21. Item 21. The solar cell glass substrate according to any one of Items 15 to 20, wherein annealing is performed after the heat treatment in a state in which a heat insulating material is disposed on a periphery of the solar cell glass substrate.
本考案に係る太陽電池用ガラス基板は、反りを抑制することができる。 The glass substrate for solar cells according to the present invention can suppress warpage.
以下、本発明に係る太陽電池用ガラス基板の一実施形態について、図面を参照しつつ説明する。 Hereinafter, one embodiment of a glass substrate for a solar cell according to the present invention will be described with reference to the drawings.
＜１．太陽電池用ガラス基板の概要＞
図１は、本実施形態に係る太陽電池用ガラス基板の断面図である。図１に示すように、この太陽電池用ガラス基板（以下、単に「ガラス基板」ということがある）は、ガラス板１と、このガラス板１の上面に形成される導電膜２と、この導電膜２の表面に被覆される機能膜３と、を備えている。以下、各部材について説明する。
<1. Overview of glass substrates for solar cells>
FIG. 1 is a cross-sectional view of a glass substrate for a solar cell according to this embodiment. As shown in FIG. 1, this glass substrate for solar cells (hereinafter sometimes simply referred to as “glass substrate”) includes a glass plate 1, a conductive film 2 formed on the upper surface of the glass plate 1, and this conductive material. And a functional film 3 coated on the surface of the film 2. Hereinafter, each member will be described.
＜１−１．ガラス板＞
ガラス板１は、透明のフロート板ガラスなど、種々のガラスにより形成することができる。また、このガラス板１は、平坦に形成されており、厚みは、例えば、例えば、０．５〜１．６ｍｍであることが好ましく、０．５〜１．１ｍｍであることがさらに好ましく、０．５〜０．８ｍｍであることが特に好ましい。
<1-1. Glass plate>
The glass plate 1 can be formed of various glasses such as a transparent float plate glass. Moreover, this glass plate 1 is formed flat, and the thickness is, for example, preferably 0.5 to 1.6 mm, more preferably 0.5 to 1.1 mm. It is especially preferable that it is 5-0.8 mm.
ガラス板１の組成は、従来の型板ガラス、建築用板ガラス、自動車用板ガラスなどの組成と同じであってもよい。具体的には、公知のソーダライムシリケートガラス、アルミノシリケートガラス、リチウムアルミノシリケートガラス、石英ガラス、ホウケイ酸ガラス、無アルカリガラス等を用いることができる。 The composition of the glass plate 1 may be the same as the composition of conventional template glass, architectural glass, automotive glass, and the like. Specifically, known soda lime silicate glass, aluminosilicate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, or the like can be used.
＜１−２．導電膜＞
導電膜２は、透明の種々の材料で形成することができるが、例えば、酸化スズ、酸化チタン、酸化亜鉛、二酸化ケイ素などで形成することができ、いずれもフッ素を含有したもの（ドープしたもの）とすることができる。例えば、酸化スズにより導電膜２を形成する場合、導電膜２における酸化スズの割合が、９０ｍｏｌ％以上であることが好ましく、９５ｍｏｌ％以上であることがさらに好ましい。一方、フッ素の割合は、０．０１〜４ｍｏｌ％であることが好ましく、０．０２〜２ｍｏｌ％であることがさらに好ましい。
<1-2. Conductive film>
The conductive film 2 can be formed of various transparent materials. For example, the conductive film 2 can be formed of tin oxide, titanium oxide, zinc oxide, silicon dioxide, etc., all containing fluorine (doped one) ). For example, when the conductive film 2 is formed of tin oxide, the ratio of tin oxide in the conductive film 2 is preferably 90 mol% or more, and more preferably 95 mol% or more. On the other hand, the proportion of fluorine is preferably 0.01 to 4 mol%, and more preferably 0.02 to 2 mol%.
導電膜２の膜厚は、０．２〜１．０μｍであることが好ましく、０．２〜０．６μｍであることがさらに好ましく、０．２〜０．４μｍであることが特に好ましい。これは、導電膜２の膜厚によって抵抗値が変化するからであり、このような厚みにすることで、例えば、膜抵抗値を８〜２５Ω／□にすることができる。 The film thickness of the conductive film 2 is preferably 0.2 to 1.0 μm, more preferably 0.2 to 0.6 μm, and particularly preferably 0.2 to 0.4 μm. This is because the resistance value varies depending on the film thickness of the conductive film 2. By setting the thickness to such a thickness, for example, the film resistance value can be set to 8 to 25Ω / □.
導電膜２の表面には、必要に応じて、微細な凹凸を形成することができる。具体的には、例えば、深さが２５〜２００ｎｍ、さらに好ましくは深さが３０〜１５０ｎｍの凹凸を形成することができる。ここでいう凹凸の深さとは、最大凸部（導電膜２の厚さ方向に対して最も突出している凸部）と最大凹部（導電膜２の厚さ方向に対して最も深く窪んだ凹部）との間の、導電膜２の厚さ方向における距離が２５〜２００ｎｍの範囲内であるということを意味する。以下、凹凸の深さが記載されている場合は、前記内容を意味する。 Fine irregularities can be formed on the surface of the conductive film 2 as necessary. Specifically, for example, irregularities having a depth of 25 to 200 nm, more preferably a depth of 30 to 150 nm can be formed. The depth of the unevenness here means the maximum convex portion (the convex portion that protrudes most in the thickness direction of the conductive film 2) and the maximum concave portion (the concave portion that is deepest in the thickness direction of the conductive film 2). It means that the distance in the thickness direction of the conductive film 2 is in the range of 25 to 200 nm. Hereinafter, when the depth of unevenness is described, it means the content described above.
上記のような凹凸は、種々の方法で形成することができるが、例えば、次のような方法で形成することができる。以下、上記のような凹凸を形成するための導電膜２の製造方法の一例について説明する。ここでは、例としてフッ素を含有する酸化スズにより導電膜２を形成する場合について説明する。 The unevenness as described above can be formed by various methods. For example, the unevenness can be formed by the following method. Hereinafter, an example of the manufacturing method of the electrically conductive film 2 for forming the above unevenness | corrugations is demonstrated. Here, the case where the electrically conductive film 2 is formed with the tin oxide containing a fluorine is demonstrated as an example.
この製造方法は、以下の工程を含む。
・溶融したガラス原料を、溶融金属上でガラスリボンへと成形する。
・溶融金属上のガラスリボンの表面に、スズ化合物、水（水蒸気）、酸素、フッ化水素を含有する原料ガスを吹き付ける。スズ化合物は、四塩化スズ等の無機スズ化合物、またはモノブチル三塩化スズ、ジメチルジクロライドスズを代表例とする有機スズ化合物を用いることができる。また、このときの処理温度は、例えば、５５０〜７５０℃とすることができる。
This manufacturing method includes the following steps.
-The molten glass raw material is formed into a glass ribbon on the molten metal.
-A raw material gas containing a tin compound, water (water vapor), oxygen, and hydrogen fluoride is sprayed on the surface of the glass ribbon on the molten metal. As the tin compound, an inorganic tin compound such as tin tetrachloride, or an organic tin compound such as monobutyltin trichloride or dimethyl dichloride tin can be used. Moreover, the process temperature at this time can be 550-750 degreeC, for example.
この方法は、例えば図２に示す装置を用いて実施できる。まず、フロート窯５１で溶融されたガラス原料（溶融ガラス）は、フロート窯５１からフロートバス５２に流れ出し、ガラスリボン１００となって溶融錫（溶融金属）５５上を移動して半固形となった後、ローラ５７により引き上げられて徐冷炉５３へと送り込まれる。徐冷炉５３で固形化したガラスリボンは、図示を省略する切断装置によって所定の大きさのガラス板１へと切断される。 This method can be implemented, for example, using the apparatus shown in FIG. First, the glass raw material (molten glass) melted in the float kiln 51 flows out from the float kiln 51 to the float bath 52 and becomes a glass ribbon 100 and moves on the molten tin (molten metal) 55 to become a semi-solid. Thereafter, the roller 57 is pulled up and fed into the slow cooling furnace 53. The glass ribbon solidified in the slow cooling furnace 53 is cut into a glass plate 1 having a predetermined size by a cutting device (not shown).
溶融錫５５上の高温状態のガラスリボン１００の表面から所定距離を隔てて、所定個数のコータ５６（図示した装置では３つのコータ５６ａ，５６ｂ，５６ｃ）が、フロートバス５２内に配置されている。これらのコータ５６ａ〜５６ｃの少なくとも１つのコータから、ガラスリボン１００上に連続的に、上述した原料ガスが供給される。これにより、ガラスリボン１００の表面に、フッ素を含有した酸化スズの結晶が形成され、これが成長することで、導電膜２が形成される。そして、この過程において、酸化スズの表面に凹凸を形成することができる。なお、導電膜２の厚みや凹凸の深さは、原料ガスの濃度、温度、処理時間を適宜変更することで、調整することができる。 A predetermined number of coaters 56 (three coaters 56 a, 56 b, 56 c in the illustrated apparatus) are arranged in the float bath 52 at a predetermined distance from the surface of the glass ribbon 100 in a high temperature state on the molten tin 55. . The above-described source gas is continuously supplied onto the glass ribbon 100 from at least one of the coaters 56a to 56c. Thereby, the crystal | crystallization of the tin oxide containing a fluorine is formed in the surface of the glass ribbon 100, and the electrically conductive film 2 is formed when this grows. In this process, irregularities can be formed on the surface of the tin oxide. The thickness of the conductive film 2 and the depth of the unevenness can be adjusted by appropriately changing the concentration, temperature, and processing time of the source gas.
その他、導電膜２は、スパッタリング法、ＣＶＤ法等の公知の方法で積層することができる。 In addition, the electrically conductive film 2 can be laminated | stacked by well-known methods, such as sputtering method and CVD method.
＜１−３．機能膜＞
機能膜３は、例えば、以下のような太陽電池の種類により種々の材料で形成することができる。
・色素を担持した多孔質半導体層（色素増感型太陽電池）
・Ｃｄｓ窓層とＣｄＴｅ光吸収層の積層体（ＣｄＴｅ太陽電池）
本実施形態に係る太陽電池用ガラス基板は、上述したように、ガラス板１に導電膜２を積層したもの（以下、中間基板１０という）を準備し、その後、太陽電池の種類に応じて、機能膜を積層する。以下、上記各太陽電池における機能膜の積層について説明する。
<1-3. Functional membrane>
The functional film 3 can be formed of various materials, for example, depending on the type of solar cell as follows.
・ Porous semiconductor layer carrying dye (dye-sensitized solar cell)
-Laminated body of Cds window layer and CdTe light absorption layer (CdTe solar cell)
As described above, the solar cell glass substrate according to the present embodiment is prepared by laminating the conductive film 2 on the glass plate 1 (hereinafter referred to as the intermediate substrate 10), and then, depending on the type of the solar cell, A functional film is laminated. Hereinafter, the lamination of the functional films in each of the solar cells will be described.
＜２．色素増感型太陽電池用ガラス基板の作製＞
色素増感型太陽電池用ガラス基板は、種々の方法で作成することができるが、以下、一例を挙げる。まず、中間基板１０に対し、酸化チタン、酸化亜鉛等の金属微粒子を積層し、例えば、１〜１０μｍ、好ましくは３〜７μｍの厚みの多孔質半導体層（機能膜）３を形成する。多孔質半導体層の形成方法は、特には限定されないが、例えば、コーティング法等の公知の方法を採用することができる。このとき、金属微粒子を塗布した後、熱処理（焼成）を行う。熱処理の温度は、例えば、４８０〜５８０℃であるが好ましく、５００〜５５０℃であることが好ましい。但し、後述するように、加熱温度は低い方が、ガラス基板の反りが小さいため、好ましい。また、熱処理の時間は、例えば、１０〜２００分であることが好ましく、３０〜１２０分であることがさらに好ましい。但し、後述するように、加熱時間は短い方が、ガラス基板の反りが小さいため、好ましい。さらに、加熱を開始してから上記加熱温度までの昇温時間は、４℃／分以上、１００℃／分以上、あるいは１５０℃／分以上とすることができる。但し、後述するように、昇温時間は短い方が、ガラス基板の反りが小さいため、好ましい。
<2. Preparation of glass substrate for dye-sensitized solar cell>
Although the glass substrate for dye-sensitized solar cells can be produced by various methods, an example will be given below. First, metal fine particles such as titanium oxide and zinc oxide are laminated on the intermediate substrate 10 to form a porous semiconductor layer (functional film) 3 having a thickness of 1 to 10 μm, preferably 3 to 7 μm, for example. Although the formation method of a porous semiconductor layer is not specifically limited, For example, well-known methods, such as a coating method, are employable. At this time, after applying the metal fine particles, heat treatment (firing) is performed. The temperature of the heat treatment is, for example, preferably 480 to 580 ° C., and preferably 500 to 550 ° C. However, as will be described later, it is preferable that the heating temperature is lower because the warpage of the glass substrate is smaller. In addition, the heat treatment time is preferably, for example, 10 to 200 minutes, and more preferably 30 to 120 minutes. However, as will be described later, it is preferable that the heating time is short because the warpage of the glass substrate is small. Furthermore, the temperature raising time from the start of heating to the heating temperature can be 4 ° C./min or more, 100 ° C./min or more, or 150 ° C./min or more. However, as will be described later, it is preferable that the heating time is shorter because the warpage of the glass substrate is smaller.
また、加熱後の徐冷時には、ガラス基板を種々の配置にすることができるが、例えば、図３に示すように、多孔質半導体層３を上方に向け、ガラス板１を石英基板５上に配置することができる。これにより、ガラス板１が石英基板５により冷却されるため、ガラス板１の収縮が抑制され、その結果、反りが抑制される。または、図４に示すように、多孔質半導体層３が石英基板５と接するようにガラス基板を配置することができる。あるいは、図５に示すように、ガラス板１の周縁の少なくとも一部を支持部材８によって支持した状態で加熱を行うことができる。このように、ガラス基板の下方に空間を形成した状態で加熱を行うと、ガラス基板が自重で撓むため、多孔質半導体層３の上方へ凸の変形と相殺され、ガラス基板全体としての反りを抑制することができる。また、徐冷時には、ガラス基板の下方に空間が形成され、下方からも空冷されるため、ガラスの収縮が抑制され、これによっても反りを抑制することができる。 In addition, during slow cooling after heating, the glass substrate can be arranged in various ways. For example, as shown in FIG. 3, the porous semiconductor layer 3 faces upward and the glass plate 1 is placed on the quartz substrate 5. Can be arranged. Thereby, since the glass plate 1 is cooled by the quartz substrate 5, the shrinkage | contraction of the glass plate 1 is suppressed and, as a result, curvature is suppressed. Alternatively, as shown in FIG. 4, the glass substrate can be disposed so that the porous semiconductor layer 3 is in contact with the quartz substrate 5. Alternatively, as shown in FIG. 5, heating can be performed in a state where at least a part of the peripheral edge of the glass plate 1 is supported by the support member 8. As described above, when heating is performed in a state where a space is formed below the glass substrate, the glass substrate is bent by its own weight, so that it is offset by the upward convex deformation of the porous semiconductor layer 3 and warps as the entire glass substrate. Can be suppressed. Moreover, at the time of slow cooling, since a space is formed below the glass substrate and air cooling is also performed from below, the shrinkage of the glass is suppressed, and thus the warpage can be suppressed.
また、徐冷時には、図６に示すように、ガラス基板の周縁に保温材６を配置することが好ましい。これにより、ガラス基板の反りがさらに低減される。なお、保温材６は、ガラス基板の上面及び下面の少なくとも一方に配置すればよいが、ガラス基板の上面にのみ配置することがさらに好ましい。 Moreover, at the time of slow cooling, as shown in FIG. 6, it is preferable to arrange | position the heat insulating material 6 to the periphery of a glass substrate. Thereby, the curvature of a glass substrate is further reduced. The heat insulating material 6 may be disposed on at least one of the upper surface and the lower surface of the glass substrate.
こうして、熱処理が終了した後、多孔質半導体層３に、色素を担持（吸着）させる。そのような色素としては、例えば、シアニン色素、メロシアニン色素、オキソノール色素、キサンテン色素、スクワリリウム色素、ポリメチン色素、クマリン色素、リボフラビン色素、ペリレン色素等の有機色素；鉄、銅、ルテニウム等の金属のフタロシアニン錯体やポルフィリン錯体等の金属錯体色素等を挙げることができる。こうして、色素増感型太陽電池用ガラス基板が完成する。なお、以上は、色素増感型太陽電池用ガラス基板の作製方法の一例であり、その工程は適宜変更することができる。 Thus, after the heat treatment is completed, the dye is supported (adsorbed) on the porous semiconductor layer 3. Examples of such dyes include organic dyes such as cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, and perylene dyes; metal phthalocyanines such as iron, copper, and ruthenium dyes. And metal complex dyes such as complexes and porphyrin complexes. In this way, the glass substrate for dye-sensitized solar cells is completed. In addition, the above is an example of the preparation method of the glass substrate for dye-sensitized solar cells, The process can be changed suitably.
＜３．ＣｄＴｅ太陽電池用ガラス基板の作製＞
ＣｄＴｅ太陽電池用ガラス基板は、種々の方法で作成することができるが、以下、一例を挙げる。まず、中間基板１０に対し、ＣＢＤ法、ＭＯＣＶＤ法などによって１００ｎｍ以下の厚さのＣｄＳ窓層３１(図７参照)を積層する。次に、ＣＳＳ法によって、例えば、１〜１０μｍ、好ましくは３〜７μｍの厚みのＣｄＴｅ層３２(図７参照)を積層する。ＣＳＳ法とは、高温に保った化合物のソース（ＣｄＴｅ）と中間基板１０とを近接して向かい合わせ、ソースを昇華させて中間基板に積層する方法である。その後、必要に応じてＣｄＣｌ2処理を行ってＣｄＴｅ層の高品質化を行う。ＣｄＴｅ層を積層する際には、上述した色素増感型太陽電池用ガラス基板の作製と同様の条件（加熱時間、加熱温度、昇温時間、徐冷方法等）で熱処理を行う。こうして、図７に示すように、ＣｄＴｅ太陽電池用ガラス基板が完成する。なお、以上は、ＣｄＴｅ太陽電池用ガラス基板の作製方法の一例であり、その工程は適宜変更することができる。
<3. Production of glass substrate for CdTe solar cell>
Although the glass substrate for CdTe solar cells can be produced by various methods, an example will be given below. First, a CdS window layer 31 (see FIG. 7) having a thickness of 100 nm or less is laminated on the intermediate substrate 10 by CBD method, MOCVD method or the like. Next, a CdTe layer 32 (see FIG. 7) having a thickness of, for example, 1 to 10 μm, preferably 3 to 7 μm is laminated by the CSS method. The CSS method is a method in which a source (CdTe) of a compound kept at a high temperature and the intermediate substrate 10 face each other close to each other, and the source is sublimated and laminated on the intermediate substrate. Thereafter, CdCl 2 treatment is performed as necessary to improve the quality of the CdTe layer. When laminating the CdTe layer, heat treatment is performed under the same conditions (heating time, heating temperature, temperature rising time, slow cooling method, etc.) as those for producing the above-described dye-sensitized solar cell glass substrate. In this way, as shown in FIG. 7, the glass substrate for CdTe solar cells is completed. In addition, the above is an example of the production method of the glass substrate for CdTe solar cells, and the process can be changed as appropriate.
＜４．ガラス基板の反りの低減の検討＞
上述した中間基板１０は、ガラス板１上に酸化スズ等で形成された導電膜２が積層されているが、機能膜３を積層する際には、熱処理が行われるため、ガラス板１及び導電膜２が熱の影響を受けて、ガラス基板に反りが生じるおそれがある。これは、ガラス板１は非結晶構造であるため、熱によって縮むのに対し、酸化スズ等の導電膜２は結晶構造であるため、熱によってほとんど縮まないからである。具体的には、ガラスの線膨張係数は約３．０×１０-6（１／Ｋ）であるのに対し、酸化スズの線膨張係数は、約９．０×１０-6（１／Ｋ）であり、このような線膨張係数の相違によって、ガラス基板に反りが生じるおそれがある。したがって、機能膜３を積層する際の熱処理によって、ガラス基板に生じる反りを抑制することが必要となる。本発明者は、ガラス基板に反りが生じるのを抑制するため、以下の通り、鋭意検討した。なお、以下では、試験を簡易化するため、機能膜３を積層することなく、中間基板１０を種々の条件で熱処理したときに生じる反りについて検討した。なお、本発明者は、これを太陽電池用ガラス基板に生じる反りとおおむね等価であることを確認している。また、以下の検討では、導電膜２の代表例として酸化スズを用いているが、線膨張係数がガラス板と相違する材料であれば、他の材料においても同様の結果が得られる。
<4. Study on reduction of glass substrate warpage>
In the above-described intermediate substrate 10, the conductive film 2 formed of tin oxide or the like is laminated on the glass plate 1. When the functional film 3 is laminated, heat treatment is performed. The film 2 may be warped due to the influence of heat. This is because the glass plate 1 has an amorphous structure and shrinks due to heat, whereas the conductive film 2 made of tin oxide or the like has a crystalline structure and therefore hardly shrinks due to heat. Specifically, the linear expansion coefficient of glass is about 3.0 × 10 −6 (1 / K), whereas the linear expansion coefficient of tin oxide is about 9.0 × 10 −6 (1 / K). And the difference in linear expansion coefficient may cause warpage of the glass substrate. Therefore, it is necessary to suppress the warp generated in the glass substrate by the heat treatment when the functional film 3 is laminated. In order to suppress the occurrence of warpage in the glass substrate, the present inventor has intensively studied as follows. In the following, in order to simplify the test, the warpage generated when the intermediate substrate 10 was heat-treated under various conditions without laminating the functional film 3 was examined. In addition, this inventor has confirmed that this is substantially equivalent to the curvature which arises in the glass substrate for solar cells. In the following examination, tin oxide is used as a representative example of the conductive film 2, but the same result can be obtained with other materials as long as the material has a linear expansion coefficient different from that of the glass plate.
＜４−１．反りの測定＞
以下の検討では、一例として、１５０×１５０ｍｍの正方形のガラス基板に、酸化スズからなる導電膜を積層した中間基板１０を準備し、この中間基板１０について、以下のように反りを測定した。まず、図８に示すように、中間基板を導電膜が上を向くように設置面Ｓに配置した。そして、中間基板１０の表面に図９に示すように、ＸＹ座標を設定した。すなわち、Ｘ方向について、−７０ｍｍ〜＋７０ｍｍの１５点を設定し、Ｙ方向について、−７０ｍｍ〜＋７０ｍｍの１５点を設定した。こうして、中間基板１０上に２２５点の測定点を規定した。そして、２軸ロボットで中間基板１０の表面を走査し、レーザー変位計（KEYENCE社製：LK-G30）を用いて、各測定点における設置面と導電膜の表面との距離、つまり面高さを測定した。こうして得られた２２５点の面高さのうち、最大の面高さと最小の面高さとの差を反り変化量と定義した。反り変形量は、小さいことが好ましいが、例えば、０．１〜１．６ｍｍであることが好ましく、０．１〜１．０ｍｍであることがさらに好ましく、０．１〜０．５ｍｍであることがより好ましく、０．１〜０．３ｍｍであることが特に好ましい。
<4-1. Measurement of warpage>
In the following examination, as an example, an intermediate substrate 10 in which a conductive film made of tin oxide was laminated on a 150 × 150 mm square glass substrate was prepared, and the warpage of the intermediate substrate 10 was measured as follows. First, as shown in FIG. 8, the intermediate substrate was arranged on the installation surface S so that the conductive film faced upward. Then, XY coordinates were set on the surface of the intermediate substrate 10 as shown in FIG. That is, 15 points of −70 mm to +70 mm were set for the X direction, and 15 points of −70 mm to +70 mm were set for the Y direction. Thus, 225 measurement points were defined on the intermediate substrate 10. Then, the surface of the intermediate substrate 10 is scanned with a two-axis robot, and the distance between the installation surface and the surface of the conductive film at each measurement point, that is, the surface height, is measured using a laser displacement meter (manufactured by KEYENCE: LK-G30). Was measured. Of the surface heights of 225 points thus obtained, the difference between the maximum surface height and the minimum surface height was defined as the amount of warpage change. The amount of warp deformation is preferably small, but is preferably, for example, 0.1 to 1.6 mm, more preferably 0.1 to 1.0 mm, and 0.1 to 0.5 mm. Is more preferable, and 0.1 to 0.3 mm is particularly preferable.
＜４−２．導電膜の積層直後の反りに関する検討１＞
まず、ガラス板１に、上記のように導電膜２を積層した直後の中間基板１０の反りについて検討した。ここでは、０．７ｍｍの厚みのガラス板上に、４８０ｎｍ，３３０ｎｍ，及び２２０ｎｍの膜厚の導電膜２を積層した直後の、中間基板１０の反り変化量を測定したところ、図１０に示す結果が得られた。同図に示すように、導電膜２の膜厚が小さいほど、反り変化量が小さいことが分かった。なお、以下の検討では、４８０ｎｍ，３３０ｎｍ，及び２２０ｎｍの膜厚の導電膜を第１導電膜、第２導電膜、第３導電膜と称することとする。また、第１導電膜、第２導電膜、第３導電膜の膜抵抗値は、それぞれ１０Ω、１５Ω、及び２０Ωである。
<4-2. Study on warping immediately after lamination of conductive film 1>
First, the warpage of the intermediate substrate 10 immediately after the conductive film 2 was laminated on the glass plate 1 as described above was examined. Here, when the amount of warpage change of the intermediate substrate 10 was measured immediately after the conductive film 2 having a thickness of 480 nm, 330 nm, and 220 nm was laminated on a glass plate having a thickness of 0.7 mm, the result shown in FIG. was gotten. As shown in the figure, it was found that the smaller the film thickness of the conductive film 2 is, the smaller the amount of warpage change is. In the following discussion, conductive films having a thickness of 480 nm, 330 nm, and 220 nm are referred to as a first conductive film, a second conductive film, and a third conductive film. The film resistance values of the first conductive film, the second conductive film, and the third conductive film are 10Ω, 15Ω, and 20Ω, respectively.
＜４−３．導電膜の積層直後の反りに関する検討２＞
次に、ガラス板１の厚みと反り変化量との関係について検討した。ここでは、０．７ｍｍ、０．９ｍｍ、１．０ｍｍの厚みのガラス板上に、第２導電膜２を積層した直後の、中間基板１０の反り変化量を測定したところ、図１１に示す結果が得られた。同図に示すように、ガラス板１の厚みが変わっても、反り変化量はあまり変化しないことが分かった。
<4-3. Study on warping immediately after lamination of conductive film 2>
Next, the relationship between the thickness of the glass plate 1 and the amount of warpage change was examined. Here, when the amount of warpage change of the intermediate substrate 10 was measured immediately after the second conductive film 2 was laminated on a glass plate having a thickness of 0.7 mm, 0.9 mm, and 1.0 mm, the result shown in FIG. was gotten. As shown in the figure, it was found that even if the thickness of the glass plate 1 changes, the amount of change in warping does not change much.
＜４−４．ガラス板の板厚に関する検討＞
続いて、導電膜２が積層された後の、中間基板１０に対し、熱処理を行った後の反り変化量を検討した。ここでは、図１２に示すように、石英基板５上に、厚みが中間基板１０を配置し、これを加熱した。中間基板１０は、導電膜２が上を向くように配置した。そして、図１３に示すように、石英基板５及び中間基板１０を、設定温度が５００℃の電気炉に入れて急加熱し、３０分間加熱した後、電気炉から出して急冷した。ここでは、０．７ｍｍ、１．０ｍｍの２種類のガラス板を用い、これらに第２導電膜を積層した２種類の中間基板１０を準備した。結果は、図１４に示すとおりである。図１４（ａ）は、加熱処理の前後の反り変化量を示しており、図１４（ｂ）は、熱処理の前後の反り変化量の差を示している。図１４（ａ）及び図１４（ｂ）に示すように、ガラス板の厚みが大きいほど、熱処理による反り変化量が小さいことが分かった。
<4-4. Study on thickness of glass plate>
Subsequently, the amount of warpage change after the heat treatment was performed on the intermediate substrate 10 after the conductive film 2 was laminated was examined. Here, as shown in FIG. 12, an intermediate substrate 10 having a thickness was placed on a quartz substrate 5 and heated. The intermediate substrate 10 was disposed so that the conductive film 2 faced upward. Then, as shown in FIG. 13, the quartz substrate 5 and the intermediate substrate 10 were put into an electric furnace having a set temperature of 500 ° C. and rapidly heated, heated for 30 minutes, then taken out of the electric furnace and rapidly cooled. Here, two types of glass substrates of 0.7 mm and 1.0 mm were used, and two types of intermediate substrates 10 were prepared by laminating a second conductive film thereon. The results are as shown in FIG. FIG. 14A shows the amount of warpage change before and after the heat treatment, and FIG. 14B shows the difference in the amount of warpage change before and after the heat treatment. As shown in FIGS. 14 (a) and 14 (b), it was found that the greater the thickness of the glass plate, the smaller the amount of warpage change due to heat treatment.
＜４−５．導電膜の膜厚に関する検討＞
次に、導電膜２の膜厚と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第１〜第３導電膜２をそれぞれ積層した３種類の中間基板１０を準備した。そして、図１２及び図１３に示すように、加熱処理を行った。但し、図１３の温度（５００℃）のほか、電気炉の温度を５５０℃にした試験も行った。結果は、図１５及び図１６に示すとおりである。図１５（ａ）は、加熱温度が５５０℃のときの加熱処理の前後の反り変化量を示しており、図１５（ｂ）は、その熱処理の前後の反り変化量の差を示している。図１６（ａ）は、加熱温度が５００℃のときの加熱処理の前後の反り変化量を示しており、図１６（ｂ）は、その熱処理の前後の反り変化量の差を示している。これらの結果により、導電膜の膜厚が小さいほど、熱処理による反り変化量が小さいことが分かった。
<4-5. Study on film thickness of conductive film>
Next, the relationship between the film thickness of the conductive film 2 and the amount of warpage change was examined. Here, three types of intermediate substrates 10 were prepared in which a glass plate 1 having a thickness of 0.7 mm was used and each of the first to third conductive films 2 was laminated. Then, heat treatment was performed as shown in FIGS. However, in addition to the temperature of FIG. 13 (500 ° C.), a test was also conducted in which the temperature of the electric furnace was 550 ° C. The results are as shown in FIGS. FIG. 15A shows the amount of warpage change before and after the heat treatment when the heating temperature is 550 ° C., and FIG. 15B shows the difference in the amount of warpage change before and after the heat treatment. FIG. 16A shows the amount of warpage change before and after the heat treatment when the heating temperature is 500 ° C., and FIG. 16B shows the difference in the amount of warpage change before and after the heat treatment. From these results, it was found that the smaller the film thickness of the conductive film, the smaller the amount of warpage change due to heat treatment.
＜４−６．加熱時間に関する検討＞
続いて、加熱時間と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第２及び第３導電膜２を積層した２種類の中間基板１０を準備した。そして、図１２及び図１３に示すように、加熱処理を行った。但し、図１３の加熱時間（３０分）のほか、加熱時間を１０分及び６０分とした試験も行った。結果は、図１７及び図１８に示すとおりである。図１７（ａ）は、第２導電膜を積層した中間基板を用いたときの加熱処理の前後の反り変化量を示しており、図１７（ｂ）は、その熱処理の前後の反り変化量の差を示している。図１８（ａ）は、第３導電膜を積層した中間基板を用いたときの加熱処理の前後の反り変化量を示しており、図１８（ｂ）は、その熱処理の前後の反り変化量の差を示している。これらの結果により、導電膜の膜厚に関わらず、加熱時間が短いほど反り変化量が小さいことが分かった。
<4-6. Study on heating time>
Subsequently, the relationship between the heating time and the amount of warp change was examined. Here, two types of intermediate substrates 10 were prepared in which the glass plate 1 having a thickness of 0.7 mm was used and the second and third conductive films 2 were laminated. Then, heat treatment was performed as shown in FIGS. However, in addition to the heating time of FIG. 13 (30 minutes), a test was conducted in which the heating time was 10 minutes and 60 minutes. The results are as shown in FIG. 17 and FIG. FIG. 17A shows the amount of warpage change before and after the heat treatment when using the intermediate substrate laminated with the second conductive film, and FIG. 17B shows the amount of warpage change before and after the heat treatment. Showing the difference. FIG. 18A shows the amount of warpage change before and after the heat treatment when using the intermediate substrate laminated with the third conductive film, and FIG. 18B shows the amount of warpage change before and after the heat treatment. Showing the difference. From these results, it was found that the amount of warpage change is smaller as the heating time is shorter, regardless of the film thickness of the conductive film.
＜４−７．加熱温度に関する検討＞
次に、加熱温度と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第２導電膜２を積層した中間基板１０を準備した。そして、図１２及び図１３に示すように、加熱処理を行った。但し、図１３の加熱温度は、５００℃のほか、４６０℃、４８０℃、５２０℃、５４０℃、５８０℃とした。結果は、図１９に示すとおりである。図１９は、加熱処理の前後の反り変化量の差を示している。同図によると、加熱温度が低いほど、反り変化量が小さいことが分かった。
<4-7. Study on heating temperature>
Next, the relationship between the heating temperature and the amount of warpage was examined. Here, an intermediate substrate 10 in which a second conductive film 2 was laminated using a glass plate 1 having a thickness of 0.7 mm was prepared. Then, heat treatment was performed as shown in FIGS. However, the heating temperature in FIG. 13 was set to 460 ° C., 480 ° C., 520 ° C., 540 ° C., and 580 ° C. in addition to 500 ° C. The results are as shown in FIG. FIG. 19 shows the difference in warpage change before and after the heat treatment. According to the figure, it was found that the lower the heating temperature, the smaller the warpage change amount.
＜４−８．昇温時間に関する検討＞
続いて、昇温時間と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第２導電膜２を積層した中間基板１０を準備した。そして、図１２及び図１３に示すように、加熱処理を行った。但し、図１３の昇温時間、つまり５００℃に達するまでの時間を、図２０に示すように、３分（急加熱）、２時間、４時間とした。また、徐冷時間は、３時間とした。結果は、図２１に示すとおりである。図２１（ａ）は、加熱処理の前後の反り変化量を示しており、図２１（ｂ）は、その熱処理の前後の反り変化量の差を示している。これらの結果により、わずかではあるが、昇温時間を短く、急速に加熱した方が、反り変化量が小さいことが分かった。
<4-8. Study on temperature rise time>
Subsequently, the relationship between the temperature rise time and the amount of warp change was examined. Here, an intermediate substrate 10 in which a second conductive film 2 was laminated using a glass plate 1 having a thickness of 0.7 mm was prepared. Then, heat treatment was performed as shown in FIGS. However, the temperature raising time in FIG. 13, that is, the time to reach 500 ° C. was set to 3 minutes (rapid heating), 2 hours, and 4 hours as shown in FIG. The slow cooling time was 3 hours. The results are as shown in FIG. FIG. 21A shows the amount of warpage change before and after the heat treatment, and FIG. 21B shows the difference in the amount of warpage change before and after the heat treatment. From these results, it was found that the amount of change in warpage was smaller when heating time was shorter and heating was shorter, although it was slight.
＜４−９．中間基板の保持方法に関する検討＞
次に、加熱処理時の中間基板の保持方法と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第２導電膜２を積層した中間基板１０を準備した。そして、図１２に示す保持方法のほか、図２２に示すように、導電膜２と石英基板５とが接するように中間基板１０を保持したとき、及び図２３に示すように、導電膜２を上に向けるとともに、ガラス板１の４隅を支持部材（レンガ）８によって支持するように中間基板１０を保持したときについて、反り変化量を測定した。加熱時間及び加熱温度は、図１３に示すとおりである。図２４に結果を示す。図２４（ａ）は、加熱処理の前後の反り変化量を示しており、図２４（ｂ）は、その熱処理の前後の反り変化量の差を示している。これらの結果により、図２４に示すように、ガラス板１の周縁を支持するように中間基板１０を保持すると、反り変化量が小さいことが分かった。
<4-9. Study on intermediate substrate holding method>
Next, the relationship between the method for holding the intermediate substrate during the heat treatment and the amount of warpage change was examined. Here, an intermediate substrate 10 in which a second conductive film 2 was laminated using a glass plate 1 having a thickness of 0.7 mm was prepared. In addition to the holding method shown in FIG. 12, when the intermediate substrate 10 is held so that the conductive film 2 and the quartz substrate 5 are in contact as shown in FIG. 22, and as shown in FIG. The amount of warpage change was measured when the intermediate substrate 10 was held so that the four corners of the glass plate 1 were supported by support members (bricks) 8 while facing upward. The heating time and heating temperature are as shown in FIG. The results are shown in FIG. FIG. 24A shows the amount of warpage change before and after the heat treatment, and FIG. 24B shows the difference in the amount of warpage change before and after the heat treatment. From these results, as shown in FIG. 24, it was found that when the intermediate substrate 10 is held so as to support the periphery of the glass plate 1, the amount of change in warpage is small.
＜４−１０．徐冷方法に関する検討＞
続いて、中間基板１０の徐冷方法と反り変化量との関係について検討した。ここでは、０．７ｍｍの厚みのガラス板１を用い、第２導電膜２を積層した中間基板１０を準備した。そして、図１３に示す加熱処理の後、炉からガラス板１を取り出し、室温まで空冷した。また、徐冷時には、図６に示すように、中間基板１０の周縁に保温材６（新日本サーマルセラミックス製スーパーウールＨＴブランケット６ｍｍ厚）を配置した。保温材６は、図２５（ａ）に示すように、中間基板１０の上面にのみに配置したとき、図２５（ｂ）に示すように、中間基板の上面及び下面の両方に配置したとき、図２５（ｃ）に示すように、中間基板の下面にのみ配置したとき、の３種類の配置方法について試験を行った。また、中間基板１０は、いずれもガラス板の４隅を支持した状態で徐冷を行った。結果は、図２６に示すとおりである。図２６（ａ）は、加熱処理の前後の反り変化量を示しており、図２６（ｂ）は、その熱処理の前後の反り変化量の差を示している。これらの結果により、中間基板１０の上面のみを保温すると、反り変化量が小さいことが分かった。
<4-10. Study on annealing method>
Subsequently, the relationship between the slow cooling method of the intermediate substrate 10 and the amount of warpage change was examined. Here, an intermediate substrate 10 in which a second conductive film 2 was laminated using a glass plate 1 having a thickness of 0.7 mm was prepared. And after the heat processing shown in FIG. 13, the glass plate 1 was taken out from the furnace and air-cooled to room temperature. Further, at the time of slow cooling, as shown in FIG. 6, a heat insulating material 6 (New Nippon Thermal Ceramics Super Wool HT Blanket 6 mm thick) was disposed on the periphery of the intermediate substrate 10. When the heat insulating material 6 is disposed only on the upper surface of the intermediate substrate 10 as shown in FIG. 25A, when it is disposed on both the upper surface and the lower surface of the intermediate substrate, as shown in FIG. As shown in FIG. 25 (c), three types of placement methods were tested when placed only on the lower surface of the intermediate substrate. In addition, the intermediate substrate 10 was gradually cooled while supporting the four corners of the glass plate. The results are as shown in FIG. FIG. 26A shows the amount of warpage change before and after the heat treatment, and FIG. 26B shows the difference in the amount of warpage change before and after the heat treatment. From these results, it was found that when only the upper surface of the intermediate substrate 10 is kept warm, the amount of change in warpage is small.
＜４−１１．ガラス基板のサイズに関する検討＞
次に、中間基板のサイズと反り変化量との関係について検討した。ここでは、厚みが０．７ｍｍ、一辺が１５０ｍｍ及び３００ｍｍの２種類のガラス板１を用い、さらに、第１〜第３導電膜２を積層した６種類の中間基板１０を準備した。そして、図１２及び図１３に示す通り、加熱処理を行った。結果は、図２７に示すとおりである。図２７は、加熱処理の前後の反り変化量の差を示している。これらの結果により、中間基板１０のサイズが小さいほど、反り変化量が小さいことが分かった。また、２−５で検討したとおり、膜厚が小さいほど、反り変化量は小さかった。
<4-11. Study on size of glass substrate>
Next, the relationship between the size of the intermediate substrate and the amount of warp change was examined. Here, two types of glass plates 1 having a thickness of 0.7 mm, a side of 150 mm, and 300 mm were used, and six types of intermediate substrates 10 in which the first to third conductive films 2 were laminated were prepared. And heat processing was performed as shown in FIG.12 and FIG.13. The results are as shown in FIG. FIG. 27 shows the difference in warpage change before and after the heat treatment. From these results, it was found that the smaller the size of the intermediate substrate 10, the smaller the amount of change in warpage. Moreover, as examined in 2-5, the smaller the film thickness, the smaller the warpage change amount.
＜４−１２．加熱時間及び加熱温度に関する検討＞
続いて、加熱時間及び加熱温度と反り変化量との関係について検討した。ここでは、厚みが０．７ｍｍ、２００ｍｍ×３００ｍｍのガラス板１を用い、さらに、第２導電膜２を積層した中間基板１０を準備した。そして、図１２に示すように中間基板を配置し、加熱温度を５００℃及び５２５℃、加熱時間を１０分、３０分、及び６０分として、加熱処理を行った。結果は、図２８に示すとおりである。図２８は、加熱処理の前後の反り変化量の差を示している。これらの結果により、中間基板１０のサイズが変わっても、加熱温度が低いほど、また、加熱時間が短いほど、反り変化量が小さいことが分かった。
<4-12. Study on heating time and heating temperature>
Subsequently, the relationship between the heating time and the heating temperature and the amount of warp change was examined. Here, an intermediate substrate 10 in which a glass plate 1 having a thickness of 0.7 mm and 200 mm × 300 mm was used and a second conductive film 2 was further laminated was prepared. Then, as shown in FIG. 12, the intermediate substrate was disposed, and the heat treatment was performed at heating temperatures of 500 ° C. and 525 ° C., heating times of 10, 30, and 60 minutes. The results are as shown in FIG. FIG. 28 shows the difference in warpage change before and after the heat treatment. From these results, it was found that even when the size of the intermediate substrate 10 is changed, the lower the heating temperature and the shorter the heating time, the smaller the amount of warpage change.
＜５．特徴＞
以上のように、本発明者が検討を行った結果、上記した点も含め、以下の知見を得た。
（１）中間基板１０に機能膜３を積層する際に、ガラス板１を再加熱し、徐冷すると、ガラス板１の線膨張係数が高いことから、ガラス板１が収縮し、これによって反りが生じることが分かった。より詳細に説明すると、例えば、ガラス板１が製造される際に急冷されると、ガラスの組織がまだ動く余地があるのにガラス転移点以下になって硬化する。その後、ガラス板をガラス転移点麩力んで再加熱すると、ガラスの構造緩和が生じ、密度が高くなる。これがガラス板の収縮の原因になり、反りが生じる。そこで、急加熱することで、中間基板１０を高温状態に晒す時間を短くできるため、反りが低減することを見出した。
<5. Features>
As described above, as a result of the study by the present inventor, the following knowledge was obtained including the above points.
(1) When the functional film 3 is laminated on the intermediate substrate 10, when the glass plate 1 is reheated and slowly cooled, the glass plate 1 contracts and warps due to the high linear expansion coefficient of the glass plate 1. Was found to occur. More specifically, for example, when the glass plate 1 is rapidly cooled when the glass plate 1 is manufactured, the glass structure is still below the glass transition point and hardens even though there is still room for movement. Thereafter, when the glass plate is reheated with a glass transition point repulsion, the structural relaxation of the glass occurs and the density increases. This causes shrinkage of the glass plate and warpage occurs. Therefore, it has been found that the rapid heating can shorten the time for which the intermediate substrate 10 is exposed to a high temperature, thereby reducing the warpage.
（２）図５に示すように、ガラス基板の下方に空間を形成した状態で加熱を行うと、ガラス基板が自重で撓むため、機能膜３の上方へ凸の変形と相殺され、ガラス基板全体としての反りを抑制することができる。また、徐冷時には、ガラス基板の下方に空間が形成され、下方からも空冷されるため、ガラス板１を高温状態に晒す時間を短くできる。その結果、ガラスの収縮が抑制され、これによっても反りを抑制することができる。 (2) As shown in FIG. 5, when heating is performed in a state where a space is formed below the glass substrate, the glass substrate is bent by its own weight, so that it is offset by the upward convex deformation of the functional film 3. Warpage as a whole can be suppressed. Moreover, at the time of slow cooling, since a space is formed below the glass substrate and air cooling is also performed from below, the time for exposing the glass plate 1 to a high temperature state can be shortened. As a result, the shrinkage of the glass is suppressed, and the warpage can also be suppressed by this.
（３）例えば、図２９に示すように、徐冷時に、保温材６を用いると、ガラス板１の上面（導電膜２と接する面）側は、高温にさらされる時間が長くなり、熱収縮が進む（矢印１）。そして、ガラス板１の下面側の熱収縮による応力（矢印２）に矢印１の応力が加わることで、応力が打ち消し合うため、ガラス板１全体としては反りが低減することを見出した。 (3) For example, as shown in FIG. 29, when the heat insulating material 6 is used at the time of slow cooling, the upper surface of the glass plate 1 (the surface in contact with the conductive film 2) side is exposed to a high temperature, and heat shrinks. (Arrow 1). And since stress canceled each other when the stress of the arrow 1 is added to the stress (arrow 2) by the thermal contraction of the lower surface side of the glass plate 1, it discovered that curvature was reduced as the glass plate 1 whole.
そして、上記検討を通じ、中間基板１０に対する熱処理において、以下の知見が得られた。すなわち、以下の方法のいずれか１以上を適宜採用することで、ガラス基板の反りが低減できることを見出した。
・ガラス基板１の厚みが大きいほど（好ましくは０．７ｍｍ以上、より好ましくは１．０ｍｍ以上）、反り変化量は小さい傾向にある。
・導電膜２の膜厚が小さいほど（好ましくは０．６μｍ以下、より好ましくは０．４μｍ以下）、反り変化量は小さい傾向にある。
・加熱温度が低いほど（好ましくは５５０℃以下、より好ましく５００℃以下）、反り変化量は小さい傾向にある。
・加熱時間が短いほど（好ましくは３０分以下、より好ましく１５分以下）、反り変化量は小さい傾向にある。
・昇温時間が短いほど（好ましくは２時間未満、より好ましく１０分未満以下）、反り変化量は小さい傾向にある。
・導電膜２を石英基板５とは反対に向けて加熱処理をしたほうが、反り変化量は小さい。
・ガラス板１の周縁を支持した状態で加熱処理をしたほうが、反り変化量は小さい傾向にある。
・ガラス板１の周縁を保温すると、反り変化量は小さい傾向にある。
Through the above examination, the following knowledge was obtained in the heat treatment for the intermediate substrate 10. That is, it has been found that the warpage of the glass substrate can be reduced by appropriately adopting one or more of the following methods.
-As the thickness of the glass substrate 1 is larger (preferably 0.7 mm or more, more preferably 1.0 mm or more), the warpage change amount tends to be smaller.
As the film thickness of the conductive film 2 is smaller (preferably 0.6 μm or less, more preferably 0.4 μm or less), the amount of change in warping tends to be smaller.
-The lower the heating temperature (preferably 550 ° C. or lower, more preferably 500 ° C. or lower), the smaller the warp change amount is.
-The shorter the heating time (preferably 30 minutes or less, more preferably 15 minutes or less), the smaller the warpage change amount is.
-The shorter the temperature rise time (preferably less than 2 hours, more preferably less than 10 minutes), the smaller the warp change amount tends to be.
-The amount of warpage change is smaller when the conductive film 2 is heat-treated opposite to the quartz substrate 5.
-When the heat treatment is performed with the periphery of the glass plate 1 supported, the amount of warpage tends to be small.
-When the periphery of the glass plate 1 is kept warm, the amount of change in warping tends to be small.
＜６．変形例＞
以上、本発明の一実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、その趣旨を逸脱しない限りにおいて、種々の変更が可能である。また、以下の変形例は、適宜、組み合わせが可能である。
<6. Modification>
As mentioned above, although one Embodiment of this invention was described, this invention is not limited to the said embodiment, A various change is possible unless it deviates from the meaning. The following modifications can be combined as appropriate.
＜６−１＞
ガラス板１の形状は特には限定されず、種々の形状が可能である。すなわち、矩形状のほか、円形状、楕円状、多角形状、異形状など、種々の形状にすることができる。そして、ガラス板１に合わせて、導電膜及び機能膜の形状も適宜変更することができる。また、導電膜及び機能膜は、ガラス板の全体に積層されていなくてもよく、一部であってもよい。
<6-1>
The shape of the glass plate 1 is not particularly limited, and various shapes are possible. That is, in addition to a rectangular shape, various shapes such as a circular shape, an elliptical shape, a polygonal shape, and a different shape can be used. And according to the glass plate 1, the shape of an electrically conductive film and a functional film can also be changed suitably. In addition, the conductive film and the functional film may not be laminated on the entire glass plate, or may be a part.
＜６−２＞
上記実施形態では、色素増感型太陽電池及びＣｄＴｅ太陽電池用の機能膜３を挙げたが、これに限定されるものではなく、熱処理を伴って積層される機能層全般に適用することができる。
<6-2>
In the above embodiment, the functional film 3 for a dye-sensitized solar cell and a CdTe solar cell has been described. However, the functional film 3 is not limited to this, and can be applied to all functional layers laminated with heat treatment. .
１ ガラス板
２ 導電膜
３ 機能膜
１０ 中間基板
1 Glass plate 2 Conductive film 3 Functional film 10 Intermediate substrate
Claims (21)
前記ガラス板上に形成される導電膜と、
前記導電膜上に形成された機能膜と、
を備えている、太陽電池用ガラス基板。 A glass plate having a thickness of 2 mm or less;
A conductive film formed on the glass plate;
A functional film formed on the conductive film;
A glass substrate for solar cells.
前記反り変形量が、０．１〜１．０ｍｍである、請求項１に記載の太陽電池用ガラス基板。 When the solar cell glass substrate is disposed on the installation surface such that the glass plate faces the installation surface, among the surfaces of the functional film, the position at the position where the distance from the installation surface is maximum. The difference between the distance and the distance at the position where the distance from the installation surface is minimum is defined as the amount of warpage deformation,
The glass substrate for a solar cell according to claim 1, wherein the warpage deformation amount is 0.1 to 1.0 mm.
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