JP2016014189A - UV援用型化学蒸着によるポリマー基板上へのドープZnO膜の被着 - Google Patents
UV援用型化学蒸着によるポリマー基板上へのドープZnO膜の被着 Download PDFInfo
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- JP2016014189A JP2016014189A JP2015136418A JP2015136418A JP2016014189A JP 2016014189 A JP2016014189 A JP 2016014189A JP 2015136418 A JP2015136418 A JP 2015136418A JP 2015136418 A JP2015136418 A JP 2015136418A JP 2016014189 A JP2016014189 A JP 2016014189A
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- Prior art keywords
- polymer substrate
- precursor
- zinc oxide
- forming
- oxide layer
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- Granted
Links
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- 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
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/482—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using incoherent light, UV to IR, e.g. lamps
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
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Abstract
Description
R1R2Zn または R1R2Zn・[L]n
という一般式に対応してよく、式中、R1とR2は同じであるかまたは異なるものであって、アルキル基またはアリール基から選択され、Lは配位子であり、Lが多座配位子(例えば二座配位子または三座配位子)である場合にはnは1であり、Lが単座配位子である場合にはnは2である。適切な配位子としては例えば、エーテル類、アミン類、アミド類、エステル類、ケトン類などが含まれる。多座配位子は、亜鉛原子と配位することのできる2つ以上のタイプの官能基を含んでいてよい。
R1R2Zn・Lz または R1R2Zn・[R3R4N(CHR5)n(CH2)m(CHR6)nNR7R8]
という一般式の化合物が含まれ、式中、R1-8は同じまたは異なるアルキルまたはアリール基、例えばメチル、エチル、イソプロピル、n−プロピル、n−ブチル、sec−ブチル、フェニルまたは置換フェニルであり得、1つ以上のフッ素含有置換基を含んでいてよく、Lは酸素系の中性配位子、例えばエーテル、ケトンまたはエステルであり、z=0〜2である。R5とR6はHまたはアルキルまたはアリール基であり得、nは0または1であり得、nが0である場合mは1〜6であり得、nが1である場合mは0〜6であり得る。
R9 2Zn・[R10O(CH2)2O(CH2)2OR10]
という一般式のジアルキル亜鉛グリコールアルキルエーテルが含まれていてよく、式中R9は1〜4個の炭素原子を有する短鎖飽和有機基であり(2つのR9基は同じであるかまたは異なるものである)、R10は、1〜4個の炭素原子を有する短鎖飽和有機基である。好ましくは、R9は、メチルまたはエチル基であり、R10はメチル基であり、
Et2Zn・[CH3O(CH2)2O(CH2)2OCH3]
という式を有するジエチル亜鉛(DEZ)ジグリムと呼ばれる。
R9 (3-n)M(R10C(O)CR11 2C(O)R12)n または R9 3M(L)
という一般式のものを含めた1つ以上の第13族金属含有前駆体で構成されていてよく、式中M=B、Al、Ga、InまたはTlであり、R9はアルキルまたはアリールまたはハロゲン化物またはアルコキシド基であり、R10-12は同じであるかまたは異なるものであってよく、H、アルキルまたはアリール基(環状または部分および過フッ素化誘導体を含む)であり、n=0〜3であり、L=金属に配位できる中性配位子である。好ましいガリウム含有前駆体は、ジメチルガリウムヘキサフルオロアセチルアセトネート(一般にMe2Ga(hfac)と呼ばれる)である。他の適切なガリウム含有前駆体としては、ジエチルガリウム(ヘキサフルオロアセチルアセトネート)、トリメチルガリウム、トリメチルガリウム(テトラヒドロフラン)、トリエチルガリウム(テトラヒドロフラン)、ジメチルガリウム(2,2,6,6−テトラメチル−3,5−ヘプタンジオネート)、ジメチルガリウム(アセチルアセトネート)、トリス(アセチルアセトネート)ガリウム、トリス(1,1,1−トリフルオロアセチルアセトネート)ガリウム、トリス(2,2,6,6−テトラメチル−3,5−ヘプタンジオネート)ガリウムおよびトリエチルガリウムが含まれていてよい。他のガリウム含有化合物も、本発明において前駆体として使用するのに適したものであり得る。
UV−CVDによるドープZnO膜を、光化学反応容器を用いて被着させた。UV光源としてHanovia中圧水銀ランプを使用した。基板としてポリフッ化ビニリデン(PVDF)膜を冷却用石英スリーブの周囲に巻きつけ、窒素キャリアガスにより前駆体と酸化剤を反応容器内に補給した。被着時間は約1〜2分であった。膜厚は約160nmである。均一な膜厚とPVDF基板に対する優れた接着力を伴う優れたコーティングが得られたが、導電性は均一ではなかった。AlドープZnO膜は、一部の領域内で最高1×10-3Ωcmまでの導電性を有していた。図1は、膜が、90%超の透過率で可視光領域内で高い透明度を有したことを示している。
Heraeus製の高圧Heメタルハライドランプを、ポリマーおよびガラス基板上の導電性ZnO膜の低温被着におけるUV光源として使用した。図3は、ランプのスペクトルを示しており、このランプの総出力は400Wである。
Claims (12)
- ポリマー基板上にドーピングされた酸化亜鉛の透明な層を形成する方法において:
(a)亜鉛及びドーパントを含む少なくとも1つの前駆体とポリマー基板を接触させるステップと、
(b)化学蒸着の間に160〜200℃の温度において紫外線光を適用して前記少なくとも1つの前駆体を分解させ、前記ポリマー基板上に層を被着させるステップと、
を含み、
前記ドーパントがAl、Ga、In、TlおよびBからなる群から選択される少なくとも1つの金属であり、
前記ポリマー基板がフッ素ポリマー樹脂、ポリエステル類、ポリアクリレート類、ポリアミド類、ポリイミド類、ポリカーボネート類、ポリエーテルケトンケトンおよびポリメチルメタクリレートからなる群から選択され、
前記接触ステップがおよそ大気圧で実施される、前記方法。 - 前記基板が光電子デバイス用のものである、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記層が透明導電性酸化層である、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記透明導電性酸化層が1×10-3Ωcm未満の抵抗率を有する、請求項3に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- ステップ(b)が200℃未満で行われる、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- ステップ(b)が160〜200℃で行なわれる、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記少なくとも1つの前駆体がステップ(a)において気相状態で導入される、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記ポリマー基板がポリフッ化ビニリデン(PVDF)、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)およびポリメチルメタクリレート(PMMA)からなる群から選択される、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記紫外線光が前記少なくとも1つの前駆体を活性化させる、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記紫外線光の波長が180〜310nmである、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 前記方法が化学蒸着プロセスである、請求項1に記載のポリマー基板上にドーピングされた酸化亜鉛層を形成する方法。
- 請求項1〜11のいずれかに記載の方法によって得られる、ポリマー基板上に被着された酸化亜鉛を含むドープ層。
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CA2777687A1 (en) | 2011-04-21 |
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