JPH01189815A - Manufacture of transparent conductive film - Google Patents
Manufacture of transparent conductive filmInfo
- Publication number
- JPH01189815A JPH01189815A JP1330488A JP1330488A JPH01189815A JP H01189815 A JPH01189815 A JP H01189815A JP 1330488 A JP1330488 A JP 1330488A JP 1330488 A JP1330488 A JP 1330488A JP H01189815 A JPH01189815 A JP H01189815A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- spray
- substrate
- base plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000007921 spray Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 ammonium halide Chemical class 0.000 claims abstract description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 3
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 3
- 230000001476 alcoholic effect Effects 0.000 claims abstract 2
- 239000000758 substrate Substances 0.000 claims description 36
- 239000007800 oxidant agent Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004715 keto acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 47
- 239000007788 liquid Substances 0.000 abstract description 18
- 238000002834 transmittance Methods 0.000 abstract description 13
- 239000011521 glass Substances 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract description 7
- 238000005507 spraying Methods 0.000 abstract description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000005118 spray pyrolysis Methods 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100348958 Caenorhabditis elegans smf-3 gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 229910021620 Indium(III) fluoride Inorganic materials 0.000 description 1
- DAOANAATJZWTSJ-UHFFFAOYSA-N N-Decanoylmorpholine Chemical compound CCCCCCCCCC(=O)N1CCOCC1 DAOANAATJZWTSJ-UHFFFAOYSA-N 0.000 description 1
- 229910021175 SmF3 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 description 1
- RMUKCGUDVKEQPL-UHFFFAOYSA-K triiodoindigane Chemical compound I[In](I)I RMUKCGUDVKEQPL-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
【発明の詳細な説明】
の１
本発明は、透明導電膜の作製法に関するものであり、特
にスプレー熱分解法を利用した透明導電膜の作製法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (1) The present invention relates to a method for producing a transparent conductive film, and particularly to a method for producing a transparent conductive film using a spray pyrolysis method.
′ の ゛ び。 占
近年、半導体装置、液晶デイスプレー装置その他の用途
において、ガラス等のような基板上に酸化スズ、酸化イ
ンジウム等の金属酸化物の薄膜を形成する必要性が増大
している。′ of ゛bi. In recent years, there has been an increasing need to form thin films of metal oxides such as tin oxide and indium oxide on substrates such as glass in semiconductor devices, liquid crystal display devices, and other applications.
第３図に図示するように、例えばアモルファスシリコン
太陽電池ｌは、透明電極付基板２にα−３ｔ膜４及び裏
面金属６が積層されて形成されている。従って、その製
造工程は、
（１）ガラス基板２ａ上に０．２〜１．０ｇｍ程度の厚
さにて透明導電！１２ｂを製膜し透明電極付基板２を形
成する工程、
（２）プラズマＣＶＤ法にて上記透明電極付基板２上に
アモルファスシリコンを製ＭＬα−３ｉｆｉ４を形成す
る工程、
（３）スパー２夕法又は真空蒸着法を利用しＡ！ｌを０
、２１Ｌｍ程度の厚さにて上記α−３ｉ膜４上に製膜
し裏面金属６を形成する工程。As shown in FIG. 3, for example, an amorphous silicon solar cell 1 is formed by laminating an α-3T film 4 and a back metal 6 on a substrate 2 with a transparent electrode. Therefore, the manufacturing process is as follows: (1) A transparent conductive film with a thickness of about 0.2 to 1.0 gm is placed on the glass substrate 2a. 12b to form a transparent electrode-attached substrate 2, (2) a step of forming amorphous silicon MLα-3ifi4 on the transparent electrode-attached substrate 2 by plasma CVD method, (3) Spar 2 evening method. Or use vacuum evaporation method A! l to 0
, a step of forming a back metal 6 on the α-3i film 4 to a thickness of about 21 Lm.
から成る。Consists of.
上記透明電極形成工程（１）は、従来ガラス基板２ａ上
に化学気相蒸着（ＣＶＤ）法又はスプレー熱分解法にて
、例えば酸化スズ（Ｓ ｎＯ２）膜を製膜するのが一般
的であった。In the transparent electrode forming step (1), it has conventionally been common to form, for example, a tin oxide (S nO2) film on the glass substrate 2a by a chemical vapor deposition (CVD) method or a spray pyrolysis method. Ta.
化学気相蒸着（ＣＶＤ）法は、常圧での反応であり、又
コンベア炉を用いた連続プロセスが可能であり、多量生
産が容易であり、且つ大面積に均一な製膜が容易に行な
い得るといった利点を有しているが、スパッタ法等と同
様にテクスチャー構造ができ難いとう問題があった。The chemical vapor deposition (CVD) method is a reaction at normal pressure, and a continuous process using a conveyor furnace is possible, making it easy to mass produce and uniformly forming a film over a large area. However, like the sputtering method, it has the problem that it is difficult to form a textured structure.
一方、Ｌ記スプレー熱分解法は、ＣＶＤ法と同様に常圧
化でのプロセスであるために多量生産が可能であり、又
容易にテクスチャー構造とすることができ、更に、例え
ばアモルファス太陽電池を作製した場合等には、ＣＶＤ
法に比較して該方法にて製造した基板を利用した方が高
い変換効率を達成し得ることが分かった。On the other hand, since the spray pyrolysis method described in L is a process under normal pressure like the CVD method, it is possible to produce in large quantities, and it is also possible to easily form a textured structure. When fabricated, etc., CVD
It has been found that higher conversion efficiency can be achieved by using a substrate manufactured by this method than by the conventional method.
しかしながら、本発明者等の研究実験によると従来のス
プレー熱分解法にて形成されたハロゲンドープの透明導
電膜は、５００℃以上の高温では透過率８０％以上で比
抵抗も３ Ｘ ｌ Ｏ−１Ωｃｍ程度の膜が形成できる
が、４００℃以下では光透過率が６０％程度と低く、比
抵抗も５ Ｘ ｌ Ｏ−１００ｍと大キく、従って４０
０℃以下の低温で光透過率を高くし且つ比抵抗を低下せ
しめることにより十分な変換効率を有するアモルファス
太陽電池用基板の生産コストの低減をなし得ることが分
かった。However, according to research experiments conducted by the present inventors, a halogen-doped transparent conductive film formed by the conventional spray pyrolysis method has a transmittance of 80% or more and a specific resistance of 3 X l O- at high temperatures of 500°C or higher. A film with a thickness of about 1 Ωcm can be formed, but the light transmittance is as low as about 60% at temperatures below 400°C, and the specific resistance is as large as 5 x l O-100 m, so 40
It has been found that the production cost of an amorphous solar cell substrate having sufficient conversion efficiency can be reduced by increasing the light transmittance and decreasing the specific resistance at a low temperature of 0° C. or lower.
又、従来のスプレー熱分解法は膜の堆積速度が遅く生産
性の点で改善が望まれていた。Furthermore, the conventional spray pyrolysis method has a slow film deposition rate, and improvements in productivity have been desired.
１１立１１
本発明の目的は、低温で光透過率が高く且つ比抵抗が小
さい透明導電膜を形成し得るスプレー熱分解法による透
明導電膜の作製法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a transparent conductive film using a spray pyrolysis method that can form a transparent conductive film with high light transmittance and low specific resistance at low temperatures.
本発明の他の目的は、堆積速度が速く、生産性が向上し
たスプレー熱分解法による透明導電膜の作製法を提供す
ることである。Another object of the present invention is to provide a method for producing a transparent conductive film by spray pyrolysis, which has a high deposition rate and improved productivity.
ロー
上記目的は本発明によって達成される。要約すれば本発
明は、透明導電膜形成用原料物質及びハロゲン化アンモ
ニウム若しくはハロゲン化水素の水又はアルコール溶液
中に酸化剤を添加して調製したスプレー液を加熱基板上
に噴霧し、熱分解反応により該基板に透明導電膜を形成
することを特徴とする透明導電膜の作製法である。透明
導電膜形成用原料物質は、スズ、インジウム又は亜鉛と
され、酸化剤としては、過酸化水素（Ｈｚ Ｏｚ ）又
はオキソ酸、例えば亜硝酸（ＨＮＯｌ）、硝酸（ＨＮＯ
３）、過マンガン酸（８Ｍｎ０４）、クロム酸（Ｈｚ
Ｃｒ０４ ） 、過塩素酸（ＨＣｌ２）、塩素酸（ＨＣ
皇０３）、亜塩素酸（ＨＣｌＯｚ）、次亜塩素酸（）ｉ
Ｃｌ Ｏ）及びその塩類が好適に使用される。特に酸
化作用の強い過酸化水素、過マンガン酸又は過塩素酸が
好ましい。The above objects are achieved by the present invention. In summary, the present invention involves spraying a spray solution prepared by adding an oxidizing agent to a water or alcohol solution of a raw material for forming a transparent conductive film and ammonium halide or hydrogen halide onto a heated substrate, and causing a thermal decomposition reaction. This is a method for producing a transparent conductive film, characterized in that a transparent conductive film is formed on the substrate. The raw material for forming the transparent conductive film is tin, indium or zinc, and the oxidizing agent is hydrogen peroxide (HzOz) or an oxoacid such as nitrous acid (HNOl), nitric acid (HNOl), etc.
3), permanganic acid (8Mn04), chromic acid (Hz
Cr04), perchloric acid (HCl2), chloric acid (HC
03), chlorous acid (HClOz), hypochlorous acid ()i
Cl 2 O) and its salts are preferably used. Particularly preferred are hydrogen peroxide, permanganic acid, or perchloric acid, which have a strong oxidizing effect.
本発明等は、ハロゲンドープ酸化スズ、酸化インジウム
、酸化亜鉛等の透明導電膜の作製において、スプレー溶
液に、上記の如き酸化剤を添加することにより膜の酸化
度を上げてドーパント濃度を減らし、透明導電膜の透過
率を高くし得ることを見出した。又、このように酸化剤
をスプレー溶液に添加することにより透明導電膜中のキ
ャリヤ濃度は低下するが、移動度は増加し、比抵抗が低
下することが分かった。In the present invention, when producing a transparent conductive film made of halogen-doped tin oxide, indium oxide, zinc oxide, etc., the oxidizing agent as described above is added to the spray solution to increase the oxidation degree of the film and reduce the dopant concentration. It has been discovered that the transmittance of a transparent conductive film can be increased. It has also been found that by adding an oxidizing agent to the spray solution in this manner, the carrier concentration in the transparent conductive film decreases, but the mobility increases and the specific resistance decreases.
更に具体的に言えば、従来のスプレー熱分解法により得
られる透明導電膜は成膜温度が４００℃程度では厚さが
４０００スのとき、透過率は６０％程度、比抵抗は少な
くとも５×１０″１Ωｃｍ以上であるのに対して、本発
明によれば、同じ処理時間、同じ成膜温度にて厚さが７
３００大と厚くすることができ、又そのときの透過率は
８０％以上、比抵抗は４ 、 ＯＸ １０ ’Ωｃｍ以
下とすることができる。More specifically, the transparent conductive film obtained by the conventional spray pyrolysis method has a transmittance of about 60% and a resistivity of at least 5×10 when the film-forming temperature is about 400°C and the thickness is 4000 mm. According to the present invention, the thickness is 7 Ωcm or more at the same processing time and the same film forming temperature.
The thickness can be increased to 300 mm, and the transmittance can be 80% or more, and the specific resistance can be 4.0 x 10' Ωcm or less.
更に堆積速度は、上記説明にても理解されるように従来
の６．０人／Ｓに対し、ｌＯス／Ｓ以上と大きく増大す
る。このように堆積速度が向上するのはスプレー溶液中
に添加した酸化剤の酸化反応が堆積速度の促進に寄与し
ているのではないかと考えられる。Furthermore, as can be understood from the above explanation, the deposition rate is greatly increased to more than 1Os/S compared to the conventional 6.0 people/S. It is thought that the reason why the deposition rate is increased in this way is that the oxidation reaction of the oxidizing agent added to the spray solution contributes to the acceleration of the deposition rate.
又、従来スプレー熱分解法にもたらされる基板は５００
℃〜６００℃に保持する必要があったが、本発明では基
板温度を３００℃〜４００℃に保持することにより極め
て良好な導電膜を形成することができた。基板温度を低
くして熱分解反応を達成し得ることは透明導電極付基板
の生産コストの低減、ソーダライムガラス使用時の透明
導電膜へのアルカリ金属の拡散抑制といった利益がある
。これも又、スプレー溶液中に添加した酸化剤の酸化反
応に起因するものであると考えられる。Moreover, the substrates conventionally provided in the spray pyrolysis method are 500
Although it was necessary to maintain the substrate temperature between 300 and 600 degrees Celsius, in the present invention, an extremely good conductive film could be formed by maintaining the substrate temperature between 300 and 400 degrees Celsius. Achieving a thermal decomposition reaction by lowering the substrate temperature has the advantage of reducing the production cost of a substrate with a transparent conductive electrode and suppressing the diffusion of alkali metals into a transparent conductive film when soda lime glass is used. This is also believed to be due to the oxidation reaction of the oxidizing agent added to the spray solution.
本発明は種々の装置にて実施し得るが、代表的な例を図
面に即して説明する。Although the present invention can be implemented in various devices, typical examples will be explained with reference to the drawings.
第１図には空気圧スプレー装置ｌＯが図示される０本実
施例においてヒータ等にて加熱されるホットプレート１
１が設けられ、該ホットプレート１１上に、例えばガラ
ス板のような基板２ａがａｒｉａされる。該ガラス板２
ａは本発明に従えば、従来の酸化剤無添加時の５００℃
〜６５０℃と言った高温に比べれば、ホットプレー）１
１にて３００℃〜４５０℃、好ましくは３５０〜４００
℃と言った低い温度に加熱される。FIG. 1 shows a pneumatic spray device 10. In this embodiment, a hot plate 1 heated by a heater etc.
1 is provided, and a substrate 2a such as a glass plate is placed on the hot plate 11. The glass plate 2
According to the present invention, a is 500°C when no oxidizing agent is added.
Compared to the high temperature of ~650℃, it is hot play) 1
1 at 300°C to 450°C, preferably 350 to 400°C
It is heated to a low temperature such as °C.
一方、前記基板２ａ上に製膜される透明導電性形成用物
質スズ、インジウム又は亜鉛等を含んだスプレー液１２
がタンク１３からスプレー５ａｔ４のノズル１５へと送
給される。該スプレー装置１４にはコンプレッサー１６
より圧縮空気が供給され、ノズル１５からスプレー液１
２を基板２ａ上へと噴霧（スプレー）する、コンプレッ
サー１６からの圧縮空気の圧力及び流量を制御手段１７
にて制御することにより噴霧の粒径及び流量が適宜に選
択される。一般に、スプレー装Ｗ１１４にはコンブＬ／
１１サー１６から約０．５ｋｇ／ｃｒｎ”Ｇの圧縮空気
が供給され、孔径的０．５ｍｍとされるノズル１５から
、噴霧粒径が１０〜１０００１ｍとされるスプレー液噴
霧体が流量０．１〜１．Ｏｍｌ／ｓｅｃにて基板２ａ上
へと所定時間間隔にて繰返し噴霧される。On the other hand, a spray liquid 12 containing a transparent conductive material such as tin, indium, or zinc is deposited on the substrate 2a.
is fed from the tank 13 to the nozzle 15 of the spray 5at4. The spray device 14 includes a compressor 16.
compressed air is supplied from the nozzle 15, and the spray liquid 1 is
Control means 17 controls the pressure and flow rate of the compressed air from the compressor 16, which sprays 2 onto the substrate 2a.
The particle size and flow rate of the spray are appropriately selected by controlling the . Generally, spray equipment W114 includes kelp L/
Compressed air of approximately 0.5 kg/crn''G is supplied from the 11 sir 16, and a spray liquid atomizer having a spray particle diameter of 10 to 10,001 m is supplied from the nozzle 15 with a hole diameter of 0.5 mm at a flow rate of 0.1 It is repeatedly sprayed onto the substrate 2a at predetermined time intervals at ~1.0ml/sec.
第２図には本発明を実施する他の装置が例示される９本
実施例の装置２０は超音波噴射装置とされる０本実施例
では、第１図に関連して説明したと同様に、ヒータ等に
て加熱されるホットプレー）２１が設けられ、該ホット
プレー）２１上に。FIG. 2 illustrates another device for carrying out the present invention.9 The device 20 of this embodiment is an ultrasonic injection device.0 In this embodiment, the same device as described in connection with FIG. A hot plate (21) heated by a heater or the like is provided on the hot plate (21).
例えばガラス板のような基板２ａが載置される。For example, a substrate 2a such as a glass plate is placed.
該ガラス板２ａはホットプレート２１にて同様に３００
℃〜４５０℃、好ましくは３５０〜４００℃に加熱され
る０本実施例ではホットプレート２１及び基板２ａは密
閉容器２２内に配置される。The glass plate 2a is similarly heated at 300 mm on the hot plate 21.
In this embodiment, the hot plate 21 and the substrate 2a are placed in a closed container 22.
該密閉容器２２には適当な排気孔（図示せず）等が形成
されている。Appropriate exhaust holes (not shown) and the like are formed in the closed container 22.
一方、前記基板２ａ上に製膜される透明導電性形成用物
質を含んだスプレー液２３が送給ポンプ２６を介してタ
ンク２４から超音波噴射装置２５へと送給される。超音
波噴射装置２５は超音波振動発生手段１００にて超音波
振動される。又、該密閉容器２２内にはコンプレッサー
２７より流量計２８を介して同伴気体（キャリアガス）
１通常圧縮空気が供給される。On the other hand, a spray liquid 23 containing a transparent conductive forming material to be formed into a film on the substrate 2a is fed from the tank 24 to the ultrasonic spraying device 25 via the feeding pump 26. The ultrasonic injection device 25 is ultrasonically vibrated by the ultrasonic vibration generating means 100. Further, entrained gas (carrier gas) is supplied into the airtight container 22 from a compressor 27 via a flow meter 28.
1 Normally compressed air is supplied.
一般に、超音波噴射装置２５は超音波振動発生手段１０
０により出力ｌＯ〜ｓｏｏｗ、周波数２０〜１００ＫＨ
ｚの超音波上て振動され、タンク２４よりスプレー液２
３が０．１ ＮｌＯｍＪＬ／ｍｉｎの流量で供給される
０本実施例によると、スプレー液は粒径が約０．１〜１
０．４ｍの範囲内にて大略均一な粒径の霧滴が得られる
。更に、本実施例では、コンプレッサー２７から、例え
ば約０ 、５ ｋ ｇ ／ ｃ ｒｎ” Ｇの圧縮空気
が、約２１ ／ ｍ ｉｎ（標準状態）の割合で加熱基
板２ａ上に噴出される。ａ音波噴射装！１２５によって
霧化されたスプレー液２３の微粒子を直接加熱基板２ａ
上に吹付けることも可能であるが、上述のように、超音
波噴射袋Ｗ２５によって霧化されたスプレー液の微粒子
を、例えば空気のようなキャリアガスと共に基板２ｂ上
へと吹付ける方が均一な製膜が達成される。Generally, the ultrasonic jetting device 25 includes the ultrasonic vibration generating means 10.
0 output lO~soow, frequency 20~100KH
It is vibrated by the ultrasonic waves of z, and the spray liquid 2 is released from the tank 24.
According to this example, the spray liquid has a particle size of about 0.1 to 1
Mist droplets with approximately uniform particle size are obtained within a range of 0.4 m. Further, in this embodiment, compressed air of, for example, about 0.5 kg/crn''G is jetted onto the heating substrate 2a from the compressor 27 at a rate of about 21/min (standard condition).a The fine particles of the spray liquid 23 atomized by the sonic spray device!125 are directly heated to the substrate 2a.
Although it is possible to spray onto the substrate 2b, as described above, it is more uniform to spray the fine particles of the spray liquid atomized by the ultrasonic spray bag W25 onto the substrate 2b together with a carrier gas such as air. film formation is achieved.
本発明に使用する超音波噴射装置２５は、例えば特願昭
５９−７７５７２号に記載されるようなもの、或いはそ
の他当業者には周知の任意のものを使用することができ
る。As the ultrasonic jetting device 25 used in the present invention, for example, the one described in Japanese Patent Application No. 77572/1984, or any other device well known to those skilled in the art can be used.
上記各実施例にて、スプレー液は、透明導電膜形成用原
料物質として混入されるフッ化スズ（ＩＩ）（ＳｎＦｚ
）、７ｙ化スズ（ｆｆ） （ＳｍＦ３）、塩化スズ（
■）（ＳｎＣ交ｌ）、塩化スズ（ＩＴ）（Ｓ ｎｃｕ＋
）、臭化スズ（ＩＩ） （Ｓ ｎＢｒｚ）、臭化ス
ズ（ＩＴ） （Ｓ ｎＢ ｒ４ ） 、ヨウ化スズ（
ＩＩ）（ＳｎＩｚ）、ヨウ化スズ（１７） （ＳｎＩ
４）、硝酸スズ（Ｉｆｆ） （Ｓ ｎ （ＮＯ３）今
）、フッ化インジウム（ＩＩＩ） （Ｉ ｎ Ｆｌ
） 、塩化インジウム（Ｉ）（Ｉ ｎｃｊＬ）、塩化イ
ンジウム（ＩＩＩ） （Ｉ ｎｃ１３） 、臭化イン
ジウム（ｍ）（ＩｎＢｒ３）、ヨウ化インジウム（Ｉｌ
ｌ）（Ｉｎ１３）、硝酸インジウム（ｍ） （Ｉ ｎ
（ＮＯｘ ）］）、］７−／化亜鉛ＺｎＦｚ）、塩化
亜鉛（ＺｎＣＲｚ）、臭化亜鉛（ＺｎＢｒｚ）、ヨウ化
亜鉛（ＺｎＩｚ）、硝酸亜鉛（Ｚｎ（ＮＯ３）ｚ）又は
炭酸亜鉛（Ｚ ｎｃＯｘ ）と、フッ化アンモニウム又
はフッ化水素との水溶液又はアルコール溶滴とされ、更
に酸化剤として過酸化水素水（Ｈｚ ０２）、又は例え
ば亜硝酸（ＨＮＯｚ ）、硝酸（ＨＮｏ、）、過マンガ
ン酸（ＨＭｎＯ＋）、クロム酸（Ｈｚ Ｃｒｏ＋）、塩
素酸（ＨＣＪ１０３ ）、次亜塩素酸（ＨＣ１０）等の
オキソ酸及びその塩類が好適に添加されたものが使用さ
れる。このとき、透明導電膜形成用原料物質としての塩
化スズ（Ｓｎ０文４）等は０．０１−１．００モル／文
、フッ化アンモニウムは０．０１〜１．０００モル／と
され、酸化剤は体積％で１−１００％、好ましくは３〜
８％添加される。In each of the above examples, the spray liquid contains tin(II) fluoride (SnFz) mixed as a raw material for forming a transparent conductive film.
), tin 7y (ff) (SmF3), tin chloride (
■) (SnC exchange), tin chloride (IT) (Sncu+
), tin(II) bromide (S nBrz), tin bromide (IT) (S nB r4 ), tin iodide (
II) (SnIz), tin iodide (17) (SnI
4), tin nitrate (Iff) (S n (NO3) now), indium (III) fluoride (I n Fl
), indium (I) chloride (I ncjL), indium (III) chloride (I nc13), indium (m) bromide (InBr3), indium iodide (Il
l) (In13), indium nitrate (m) (I n
(NO x ) and ammonium fluoride or hydrogen fluoride in an aqueous solution or alcohol droplets, and hydrogen peroxide (Hz 02) as an oxidizing agent, or, for example, nitrous acid (HNOz), nitric acid (HNO, ), permanganic acid. (HMnO+), chromic acid (Hz Cro+), chloric acid (HCJ103), hypochlorous acid (HC10), and other oxoacids and their salts are preferably added. At this time, the amount of tin chloride (Sn0 4) used as a raw material for forming a transparent conductive film is 0.01-1.00 mol/ml, ammonium fluoride is 0.01-1.000 mol/ml, and the oxidizing agent is is 1-100% by volume, preferably 3-100%
8% added.
次に、本発明に係る方法を、半導体装置に使用される酸
化スズ膜基板の作製に適用した実施例について説明する
。Next, an example will be described in which the method according to the present invention is applied to the production of a tin oxide film substrate used in a semiconductor device.
実施例１
第１図に図示される構成の製造装置を使用して透明導電
膜を作製した。基板２ａとしては表面に５ｉＯｚアンダ
ーコートを施した１０ｃｍ角の並ガラスを用い、ホット
プレート１１上に載置し、表面温度４００℃にまで加熱
した。Example 1 A transparent conductive film was manufactured using a manufacturing apparatus having the configuration shown in FIG. As the substrate 2a, a 10 cm square ordinary glass with a 5 iOz undercoat on the surface was used, and it was placed on a hot plate 11 and heated to a surface temperature of 400°C.
スプレー液は、エタノール中に塩化スズ（ＳｎＣ父斗・
５Ｈ２Ｏ）を０．１モル／１．フッ化アンモニウム（Ｎ
Ｈ４Ｆ）を０．１モル／文に、過酸化水素水（）ｉｚ
Ｏこ濃度約３５％）を約５体積％加えた水溶液を調製し
た。The spray solution contains tin chloride (SnC) in ethanol.
5H2O) at 0.1 mol/1. Ammonium fluoride (N
H4F) to 0.1 mol/liter, hydrogen peroxide solution ()iz
An aqueous solution containing about 5% by volume of O (concentration: about 35%) was prepared.
次いで、コンプレッサー１６を作動させ、スプレー装置
１４に約０．５ｋｇ／ｃｍ″ｑの圧縮空気を供給し、孔
径的０．５ｍｍのノズル１５から、噴霧粒径がｌＯ〜１
０００Ａｎとされるスプレー液噴霧体を流量的０．３ｍ
文／ｓｅｃにて基板２ａｌ−へと噴霧した。Next, the compressor 16 is operated to supply compressed air of approximately 0.5 kg/cm''q to the spray device 14, and the sprayed particle size is 10 to 1 from the nozzle 15 with a hole diameter of 0.5 mm.
000An spray liquid atomizer with a flow rate of 0.3m
It was sprayed onto the substrate 2al- at a rate of 100 min/sec.
この噴霧を約１０秒行ない、次いで１０秒停止する噴霧
サイクルを１０回繰り返し行なった。This spraying cycle was repeated 10 times in which the spraying was continued for about 10 seconds and then stopped for 10 seconds.
基板？ａ上にフー、ｌドープ酸化スズ薄ｆｉ２ｂが約８
０００大の厚さで形成された。該薄膜の透過率は４００
〜８００ｎｍの可視域で約８０％であり、比抵抗は約３
Ｘ Ｌ Ｏ”１０ｃｍであった。substrate? Fu, L-doped tin oxide thin fi2b on a is about 8
It was formed with a thickness of 0.000 mm. The transmittance of the thin film is 400
It is about 80% in the visible range of ~800 nm, and the specific resistance is about 3
The length was 10 cm.
比較例１
過酸化水素水を全く含まない以外は実施例１と同じスプ
レー液を使用し、実施例１と同様にして透明導電膜を作
製した。Comparative Example 1 A transparent conductive film was produced in the same manner as in Example 1, using the same spray liquid as in Example 1 except that it did not contain any hydrogen peroxide solution.
このようにして作製したフッ素ドープ酸化スズ薄１１２
ｂは約５０００スの厚さしか有しておらず、又、該薄膜
の透過率は４００〜８００ｎｍの可視域で約６０％であ
り、比抵抗は約５ Ｘ １０ ’Ωｃｍであった。Fluorine-doped tin oxide thin film 112 produced in this way
b had a thickness of only about 5000 mm, the transmittance of the thin film was about 60% in the visible range from 400 to 800 nm, and the resistivity was about 5 x 10' Ωcm.
実施例２
第２図に図示される構成の製造装置を使用して透明導電
膜を作製した。基板２ａとしては表面に５ｉＯｚアンダ
ーコートを施した１０ｃｍ角の並ガラスを用い、ホット
プレート１１上に載置し、表面温度４００℃にまで加熱
された。Example 2 A transparent conductive film was manufactured using a manufacturing apparatus having the configuration shown in FIG. As the substrate 2a, a 10 cm square ordinary glass with a 5 iOz undercoat on the surface was used, and it was placed on a hot plate 11 and heated to a surface temperature of 400°C.
実施例１と同じスプレー液を用意した。該スプレー液を
ポンプ２６により超音波噴射装置２５へと約２ｍｕ／ｍ
ｉｎの流量で供給した。超音波発生手段１００を作動さ
せて出力１００Ｗ、周波数２８Ｋｌ（ｚの超音波にてス
プレー液を霧化し、粒径的ｌβｍの大略均一な粒径の噴
霧体を得た。更にコンプレッサー２７を作動させて約０
．５ｋｇ／ＣゴＧの圧縮空気を、約２ＪＬ／ｍ１ｎ（標
準状態）の割合で加熱基板２ａ上に噴出させた。この噴
霧を約１２分間継続して行なった。The same spray solution as in Example 1 was prepared. The spray liquid is transferred to the ultrasonic spray device 25 by the pump 26 at a rate of approximately 2 mu/m.
It was supplied at a flow rate of in. The ultrasonic generating means 100 was operated to atomize the spray liquid using ultrasonic waves with an output of 100 W and a frequency of 28 Kl (z) to obtain a spray having a substantially uniform particle size of lβm.Furthermore, the compressor 27 was operated. about 0
．． Compressed air of 5 kg/CG was jetted onto the heating substrate 2a at a rate of about 2 JL/m1n (standard state). This spraying was continued for about 12 minutes.
基板２ａ上にフッ素ドープ酸化スズ薄膜２ｂが約７５０
０大の厚さで形成された。該薄膜の透過率は４００〜８
００ｎｍの可視域で約８０％であり、比抵抗は約４ Ｘ
１０−３Ωｃｍであった。A fluorine-doped tin oxide thin film 2b is formed on the substrate 2a with a thickness of approximately 750 mm.
It was formed with a thickness of 0. The transmittance of the thin film is 400-8
It is about 80% in the visible range of 00 nm, and the specific resistance is about 4
It was 10-3 Ωcm.
本実施例にて作製された透明導電膜のＸ線回折図形を第
４図に示す。FIG. 4 shows the X-ray diffraction pattern of the transparent conductive film produced in this example.
比較例２
過酸化水素水を全く含まない以外は実施例２と同じスプ
レー液を使用し、実施例２と同様にして透明導電膜を作
製した。Comparative Example 2 A transparent conductive film was produced in the same manner as in Example 2, using the same spray liquid as in Example 2 except that it did not contain any hydrogen peroxide solution.
このようにして作製したフッ素ドープ酸化スズ薄膜２ｂ
は約４０００大の厚さしか有しておらず、該薄膜の透過
率は４００〜８００ｎｍの可視域で約６３％であり、比
抵抗は約６ Ｘ １０−３ΩＣｍであった。Fluorine-doped tin oxide thin film 2b produced in this way
had a thickness of only about 4000 nm, the transmittance of the thin film was about 63% in the visible range from 400 to 800 nm, and the resistivity was about 6 x 10-3 ΩCm.
本比較例にて作製された透明導電膜のＸ線回折図形を第
５図に示す、第４図と第５図を比較検討すると、酸化剤
添加により酸素を置換するフッ素が減少し、膜中ドナー
は酸素欠損が支配的となるということが分かる。The X-ray diffraction pattern of the transparent conductive film produced in this comparative example is shown in Figure 5. Comparative examination of Figures 4 and 5 reveals that the addition of an oxidizing agent reduces the amount of fluorine that replaces oxygen in the film. It can be seen that the donor is dominated by oxygen vacancies.
左」ＬＤ」Ｌｌ
以上説明したように、本発明に係る透明導電膜作製法に
よると、４００℃以下の低温で光透過率が高く且つ比抵
抗が小さい透明導電膜を形成し得、更には、堆積速度が
速く、生産性が向上するという特長を有する。Left "LD" Ll As explained above, according to the method for producing a transparent conductive film according to the present invention, a transparent conductive film with high light transmittance and low specific resistance can be formed at a low temperature of 400° C. or lower, and further, It has the advantage of fast deposition rate and improved productivity.
第１図及び第２図は、本発明に係る透明導電膜作製法を
実施するための装置の実施例を説明する概略断面図であ
る。
第３図は、アモルファスシリコン太陽電池の断面図であ
る。
第４図は、本発明に係る透明導電膜作製法にて形成され
たｓ膜のｘｍ回折図形である。
第５図は、従来の透明導電膜作製法にて形成された薄膜
のＸ線回折図形である。
２ａ：基板
２ｂ：透明導電膜
１１．２１：ホットプレート
１２．２３ニスプレー液
１４ニスプレー装置
１６：コンプレッサー
２５：超音波噴射装置
１００：超音波振動発生手段
し−二
第４図FIGS. 1 and 2 are schematic cross-sectional views illustrating an embodiment of an apparatus for carrying out the method for producing a transparent conductive film according to the present invention. FIG. 3 is a cross-sectional view of an amorphous silicon solar cell. FIG. 4 is an xm diffraction pattern of an s film formed by the method for producing a transparent conductive film according to the present invention. FIG. 5 is an X-ray diffraction pattern of a thin film formed by a conventional transparent conductive film manufacturing method. 2a: Substrate 2b: Transparent conductive film 11.21: Hot plate 12.23 Varnish spray liquid 14 Varnish spray device 16: Compressor 25: Ultrasonic spray device 100: Ultrasonic vibration generating means -2 Fig. 4
Claims (1)
ウム若しくはハロゲン化水素を含む水溶液又はアルコー
ル溶液中に酸化剤を添加して調製したスプレー液を加熱
基板上に噴霧し、熱分解反応により該基板に透明導電膜
を形成することを特徴とする透明導電膜の作製法。 ２）透明導電膜形成用原料物質は、スズ、インジウム若
しくは亜鉛のハロゲン化物、硝酸塩又は炭酸塩である特
許請求の範囲第１項記載の作製法。 ３）酸化剤は、過酸化水素（Ｈ＿２Ｏ＿２）又はオキソ
酸若しくはその塩類である特許請求の範囲第１項又は第
２項記載の作製法。[Scope of Claims] 1) A spray solution prepared by adding an oxidizing agent to an aqueous or alcoholic solution containing a raw material for forming a transparent conductive film and ammonium halide or hydrogen halide is sprayed onto a heated substrate, and then heated. A method for producing a transparent conductive film, which comprises forming a transparent conductive film on the substrate by a decomposition reaction. 2) The manufacturing method according to claim 1, wherein the raw material for forming the transparent conductive film is a halide, nitrate, or carbonate of tin, indium, or zinc. 3) The production method according to claim 1 or 2, wherein the oxidizing agent is hydrogen peroxide (H_2O_2) or an oxoacid or a salt thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330488A JPH01189815A (en) | 1988-01-22 | 1988-01-22 | Manufacture of transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330488A JPH01189815A (en) | 1988-01-22 | 1988-01-22 | Manufacture of transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01189815A true JPH01189815A (en) | 1989-07-31 |
Family
ID=11829441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1330488A Pending JPH01189815A (en) | 1988-01-22 | 1988-01-22 | Manufacture of transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01189815A (en) |
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|---|---|---|---|---|
| JP2005085699A (en) * | 2003-09-10 | 2005-03-31 | Fujikura Ltd | Apparatus for manufacturing substrate for transparent electrode |
| JP2007238393A (en) * | 2006-03-09 | 2007-09-20 | Dainippon Printing Co Ltd | Method and apparatus for producing metal oxide film |
| JP2011504293A (en) * | 2007-11-02 | 2011-02-03 | エージーシー フラット グラス ノース アメリカ，インコーポレイテッド | Transparent conductive oxide film for thin film photovoltaic application and method of manufacturing the same |
| WO2014196095A1 (en) * | 2013-06-04 | 2014-12-11 | Ｒｏｃａ株式会社 | Method for producing oxide crystal thin film |
| WO2015005202A1 (en) * | 2013-07-09 | 2015-01-15 | 株式会社Flosfia | Semiconductor device and manufacturing method for same, crystal, and manufacturing method for same |
| JP2017112345A (en) * | 2015-12-11 | 2017-06-22 | 株式会社Flosfia | Method for manufacturing silicon oxide film |
-
1988
- 1988-01-22 JP JP1330488A patent/JPH01189815A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4698939B2 (en) * | 2003-09-10 | 2011-06-08 | 株式会社フジクラ | Transparent electrode substrate manufacturing equipment |
| JP2005085699A (en) * | 2003-09-10 | 2005-03-31 | Fujikura Ltd | Apparatus for manufacturing substrate for transparent electrode |
| JP2007238393A (en) * | 2006-03-09 | 2007-09-20 | Dainippon Printing Co Ltd | Method and apparatus for producing metal oxide film |
| JP2015053494A (en) * | 2007-11-02 | 2015-03-19 | エージーシー フラット グラス ノース アメリカ，インコーポレイテッドＡｇｃ Ｆｌａｔ Ｇｌａｓｓ Ｎｏｒｔｈ Ａｍｅｒｉｃａ，Ｉｎｃ． | Transparent conductive oxide coating for thin film photovoltaic application and production method of the same |
| JP2011504293A (en) * | 2007-11-02 | 2011-02-03 | エージーシー フラット グラス ノース アメリカ，インコーポレイテッド | Transparent conductive oxide film for thin film photovoltaic application and method of manufacturing the same |
| US9181124B2 (en) | 2007-11-02 | 2015-11-10 | Agc Flat Glass North America, Inc. | Transparent conductive oxide coating for thin film photovoltaic applications and methods of making the same |
| WO2014196095A1 (en) * | 2013-06-04 | 2014-12-11 | Ｒｏｃａ株式会社 | Method for producing oxide crystal thin film |
| TWI490368B (en) * | 2013-06-04 | 2015-07-01 | Flosfia Inc | Preparation method of oxide crystal film |
| US10202685B2 (en) | 2013-06-04 | 2019-02-12 | Flosfia Inc. | Method of manufacturing oxide crystal thin film |
| WO2015005202A1 (en) * | 2013-07-09 | 2015-01-15 | 株式会社Flosfia | Semiconductor device and manufacturing method for same, crystal, and manufacturing method for same |
| JPWO2015005202A1 (en) * | 2013-07-09 | 2017-03-02 | 株式会社Flosfia | Semiconductor device and manufacturing method thereof, and crystal and manufacturing method thereof |
| US9966439B2 (en) | 2013-07-09 | 2018-05-08 | Flosfia Inc. | Semiconductor device and manufacturing method for same, crystal, and manufacturing method for same |
| JP2017112345A (en) * | 2015-12-11 | 2017-06-22 | 株式会社Flosfia | Method for manufacturing silicon oxide film |
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