JP4871777B2 - Etching solution and transistor manufacturing method - Google Patents
Etching solution and transistor manufacturing method Download PDFInfo
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- JP4871777B2 JP4871777B2 JP2007106775A JP2007106775A JP4871777B2 JP 4871777 B2 JP4871777 B2 JP 4871777B2 JP 2007106775 A JP2007106775 A JP 2007106775A JP 2007106775 A JP2007106775 A JP 2007106775A JP 4871777 B2 JP4871777 B2 JP 4871777B2
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- 238000005530 etching Methods 0.000 title claims description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000010949 copper Substances 0.000 claims description 78
- 239000010409 thin film Substances 0.000 claims description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 73
- 229910052802 copper Inorganic materials 0.000 claims description 73
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 47
- 239000005751 Copper oxide Substances 0.000 claims description 39
- 229910000431 copper oxide Inorganic materials 0.000 claims description 39
- 239000010408 film Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000059 patterning Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 41
- 229960004643 cupric oxide Drugs 0.000 description 37
- 239000007788 liquid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Electrodes Of Semiconductors (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
Description
本発明は金属のエッチングに関し、特に、トランジスタの配線膜をエッチングする技術に関する。 The present invention relates to metal etching, and more particularly to a technique for etching a wiring film of a transistor.
近年では、トランジスタの高速化のために、現状のポリシリコンのゲート電極を、低抵抗の金属のゲート電極に変更したいという要望があり、低抵抗の金属としては銅が有望視されている。
液晶表示装置の薄膜トランジスタ（ＴＦＴ）では、ゲート電極はガラス基板表面に密着して配置されるが、純銅の薄膜はガラス基板に対する接着力が弱く、剥離してしまうという問題がある。
In recent years, there has been a demand to change the current polysilicon gate electrode to a low-resistance metal gate electrode in order to increase the speed of the transistor, and copper is promising as a low-resistance metal.
In a thin film transistor (TFT) of a liquid crystal display device, a gate electrode is disposed in close contact with the surface of a glass substrate, but a thin film of pure copper has a problem that the adhesive strength to the glass substrate is weak and peels off.
他方、ＣｕＯやＣｕ2Ｏ等の銅酸化物を含有する銅酸化物薄膜は、ガラス基板に対して接着力は強いものの、抵抗値が大きいため、銅酸化物薄膜をゲート電極に採用するメリットが無い。 On the other hand, a copper oxide thin film containing a copper oxide such as CuO or Cu 2 O has a strong resistance to a glass substrate, but has a large resistance value, so there is a merit of adopting the copper oxide thin film as a gate electrode. No.
そこで、銅配線膜を、下層部分を銅酸化物薄膜、上層部分を純銅薄膜の二層構造とし、この二層構造の銅配線膜によってゲート電極や蓄積容量電極を構成させる試みがなされている。
二層構造の銅配線膜は、一般に、銅酸化物薄膜と純銅薄膜の積層膜を、エッチング液で所定形状にパターニングして形成される。
Therefore, an attempt has been made to configure the copper wiring film as a two-layer structure having a copper oxide thin film as a lower layer portion and a pure copper thin film as an upper layer portion, and to constitute a gate electrode or a storage capacitor electrode with the copper wiring film having this two-layer structure.
A copper wiring film having a two-layer structure is generally formed by patterning a laminated film of a copper oxide thin film and a pure copper thin film into a predetermined shape with an etching solution.
一般に、銅を主成分とする薄膜のエッチングには、硝酸系エッチング液、塩化第二鉄系エッチング液、過硫酸アンモニウム系エッチング液、塩化銅系エッチング液、クロム酸−硫酸系エッチング液等が用いられる。 In general, for etching a thin film containing copper as a main component, a nitric acid-based etching solution, a ferric chloride-based etching solution, an ammonium persulfate-based etching solution, a copper chloride-based etching solution, a chromic acid-sulfuric acid-based etching solution, and the like are used. .
これらの中でも、硝酸系エッチングは、ゲート電極のような薄膜のエッチングに特に優れている。硝酸系エッチング液中では、下記反応式（１）に示すように、硝酸から酸素が遊離する。
２ＨＮＯ3 → Ｈ2Ｏ＋ ２ＮＯ2 ＋ Ｏ……反応式（１）
遊離した酸素は、下記反応式（２）に示すように銅と反応して酸化銅が生成される
Ｃｕ ＋Ｏ → ＣｕＯ……反応式（２）
酸化銅は塩基性化合物であるから、下記反応式（３）に示すように硝酸と反応して硝酸銅となる。
ＣｕＯ＋２ＨＮＯ3→Ｃｕ（ＮＯ3）2 ＋ Ｈ2Ｏ……反応式（３）
硝酸系エッチング液は水溶液であり、硝酸銅は水溶液中で電離して硝酸イオンと銅イオンとなり、その結果銅がエッチング液中に溶解した状態になる。このように、銅は一旦酸化銅になってから溶解するから、銅酸化物薄膜は、純銅薄膜よりもエッチング速度が速い。
Among these, nitric acid-based etching is particularly excellent for etching a thin film such as a gate electrode. In the nitric acid-based etchant, oxygen is liberated from nitric acid as shown in the following reaction formula (1).
2HNO 3 → H 2 O + 2NO 2 + O ... Reaction formula (1)
The liberated oxygen reacts with copper to produce copper oxide as shown in the following reaction formula (2): Cu + O → CuO ... reaction formula (2)
Since copper oxide is a basic compound, it reacts with nitric acid to become copper nitrate as shown in the following reaction formula (3).
CuO + 2HNO 3 → Cu (NO 3 ) 2 + H 2 O …… Reaction formula (3)
The nitric acid-based etching solution is an aqueous solution, and copper nitrate is ionized in the aqueous solution to become nitrate ions and copper ions, and as a result, the copper is dissolved in the etching solution. Thus, since copper once becomes copper oxide and then melts, the copper oxide thin film has a higher etching rate than the pure copper thin film.
図６は積層膜１５０をレジスト層１５５の開口１５９パターンに沿って硝酸系エッチング液でパターニングした時の模式的断面図を示しており、銅酸化物薄膜１５１は、純銅薄膜１５２に比べて、開口１５９内に露出する側面がオーバーエッチングされ、積層膜１５０の下層部分の幅が狭くなるアンダーカットと呼ばれる現象が起こり、積層膜１５０の割れや、ガラス基板１５６からの剥離が起こりやすくなる。
FIG. 6 is a schematic cross-sectional view when the laminated
また、硝酸系エッチング液に変え、上述した塩化第二鉄系エッチング液、過硫酸アンモニウム系エッチング液、塩化銅系エッチング液、クロム酸−硫酸系エッチング液等を用いてもアンダーカット現象は生じ、同じエッチング液でアンダーカットを起こさずに、銅酸化物の含有量の異なる銅薄膜をエッチングするのは困難であった。
本発明は上記課題を解決するために成されたものであり、その目的は割れや剥離を起こさずに積層膜をエッチングする技術を提供することである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a technique for etching a laminated film without causing cracking or peeling.
本発明者等が、硝酸系エッチング液を希釈して積層膜のエッチングを行ったところ、エッチング速度が遅くなる上、純銅薄膜と銅酸化物薄膜のエッチング速度の差は逆に大きくなり、アンダーカット現象は防止されなかった。 When the inventors of the present invention diluted the nitric acid-based etchant to etch the laminated film, the etching rate was slow, and the difference in the etching rate between the pure copper thin film and the copper oxide thin film increased conversely, resulting in an undercut. The phenomenon was not prevented.
本発明者等が更に鋭意検討を行ったところ、硝酸系エッチング液に、燐酸と、塩酸とを添加すれば、純銅膜と銅酸化薄膜のエッチング速度の差が縮まり、アンダーカット現象が防止されることを見出した。 As a result of further intensive studies by the present inventors, if phosphoric acid and hydrochloric acid are added to the nitric acid-based etching solution, the difference in etching rate between the pure copper film and the copper oxide thin film is reduced, and the undercut phenomenon is prevented. I found out.
係る知見に基づいて成された本発明は、銅酸化物を含有する第一の銅薄膜と、前記第一の銅薄膜よりも前記銅酸化物の含有量が少ない第二の銅薄膜とが積層された積層膜のエッチングに用いるエッチング液であって、硫酸と、硝酸と、酢酸と、塩酸と、燐酸とを含有する水溶液で構成されたエッチング液である。
本発明は、ゲート電極と、ゲート絶縁膜と、チャネル半導体層と、ドレイン半導体層と、ソース半導体層とを有し、前記ゲート電極は、ガラス基板の表面に密着する第一の銅薄膜と、前記第一の銅薄膜の表面に配置され、前記第一の銅薄膜よりも銅酸化物の含有量が少なくされた第二の銅薄膜とからなる積層膜を、パターニングして形成された薄膜トランジスタを製造する薄膜トランジスタ製造方法であって、前記積層膜の前記第二の銅薄膜の表面に、所定形状の開口が形成されたレジスト層を配置し、前記開口の底面に露出する前記積層膜に、硫酸と、硝酸と、酢酸と、燐酸と、塩酸とを含有する水溶液からなるエッチング液を接触させて前記積層膜をパターニングするトランジスタ製造方法である。
The present invention made on the basis of such knowledge is a lamination of a first copper thin film containing a copper oxide and a second copper thin film containing less copper oxide than the first copper thin film. An etching solution used for etching the laminated film is an etching solution composed of an aqueous solution containing sulfuric acid, nitric acid, acetic acid, hydrochloric acid, and phosphoric acid.
The present invention includes a gate electrode, a gate insulating film, a channel semiconductor layer, a drain semiconductor layer, and a source semiconductor layer, the gate electrode being in close contact with the surface of the glass substrate; A thin film transistor formed by patterning a laminated film that is disposed on the surface of the first copper thin film and is made of a second copper thin film that contains less copper oxide than the first copper thin film. A method of manufacturing a thin film transistor, comprising: disposing a resist layer having an opening having a predetermined shape on a surface of the second copper thin film of the stacked film; and applying sulfuric acid to the stacked film exposed on a bottom surface of the opening And a method of manufacturing a transistor in which the stacked film is patterned by bringing an etching solution made of an aqueous solution containing nitric acid, acetic acid, phosphoric acid, and hydrochloric acid into contact with each other.
本発明は上記のように構成されており、本発明のエッチング液の構成材料のうち、硝酸が銅を溶解する溶解成分であり、硝酸は銅を酸化させてから溶解するので、硝酸に対する溶解速度（エッチング速度）は、銅酸化物の含有量が多い程早くなる。
燐酸と塩酸は単体では銅を不溶（難溶）であるが、エッチング液に燐酸と塩酸を加えると、純銅のエッチング速度を遅くせず、銅酸化物のエッチング速度を遅くする。
The present invention is configured as described above, and among the constituent materials of the etching solution of the present invention, nitric acid is a dissolving component that dissolves copper, and nitric acid dissolves after oxidizing copper, so the dissolution rate in nitric acid (Etching rate) increases as the copper oxide content increases.
Phosphoric acid and hydrochloric acid alone are insoluble (slightly soluble) in copper. However, when phosphoric acid and hydrochloric acid are added to the etching solution, the etching rate of pure copper is not slowed, and the etching rate of copper oxide is slowed.
従って、銅酸化物のエッチング速度は純銅のエッチング速度に対して遅くなり、エッチング速度の差が小さくなるので、第一、第二の銅薄膜の積層膜を膜厚方向にエッチングする際に、アンダーカットが起こりにくくなる。 Accordingly, the etching rate of the copper oxide is slower than the etching rate of pure copper, and the difference between the etching rates is reduced. Therefore, when etching the laminated film of the first and second copper thin films in the film thickness direction, Cut is less likely to occur.
尚、塩酸は銅酸化物のエッチング速度を減速し、燐酸は銅酸化物のエッチング速度を加速する傾向があるので、塩酸と燐酸の含有量を変えることで、酸化銅のエッチング速度を調整することができる。 Since hydrochloric acid tends to slow down the etching rate of copper oxide and phosphoric acid tends to accelerate the etching rate of copper oxide, the etching rate of copper oxide can be adjusted by changing the contents of hydrochloric acid and phosphoric acid. Can do.
硫酸と酢酸は単体では銅を不溶（難溶）であるが、ｐＨ緩衝効果があり、エッチング液に添加すると、エッチング液のｐＨが所定値で安定する。
尚、本発明で第一、第二の銅薄膜は、銅を主成分とする膜であって、金属元素として銅だけを含有する場合と、銅を主成分とし、Ｚｒ、Ｍｇ、Ｎｉ、Ｔｉ等他の添加金属を１種類以上含有する場合とがある。
Although sulfuric acid and acetic acid alone are insoluble (slightly soluble) in copper, they have a pH buffering effect, and when added to an etching solution, the pH of the etching solution is stabilized at a predetermined value.
In the present invention, the first and second copper thin films are films containing copper as a main component, and contain only copper as a metal element, and include copper as a main component, Zr, Mg, Ni, Ti. In some cases, it contains one or more other additive metals.
本発明のエッチング液は、第一、第二の銅薄膜が添加金属を含有する場合も、添加金属を含有しない場合と比べてエッチング速度が変わらないので、エッチングの際にアンダーカットが起こらない。
本発明のエッチング液には、必要に応じて、界面活性剤、他のｐＨ緩衝剤等の添加剤を添加することもできる。
In the etching solution of the present invention, even when the first and second copper thin films contain an additive metal, the etching rate does not change as compared with the case where the additive metal does not contain an additive metal.
If necessary, additives such as surfactants and other pH buffering agents can be added to the etching solution of the present invention.
銅酸化物薄膜と純銅薄膜のエッチング速度の差を縮め、アンダーカットを防止する。基板から剥離し難く、割れの無い銅電極が形成されるので、ＴＦＴの信頼性が高い。 The etching rate difference between the copper oxide thin film and the pure copper thin film is reduced to prevent undercutting. Since a copper electrode that does not easily peel from the substrate and does not crack is formed, the reliability of the TFT is high.
本発明方法を図面を用いて説明する。
図１（ａ）の符号１０は処理対象基板を示しており、処理対象基板１０は、ガラス基板１１と、ガラス基板１１の表面に形成された第一の銅薄膜５１と、第一の銅薄膜５１の表面に形成された第二の銅薄膜５２とを有している。
The method of the present invention will be described with reference to the drawings.
The code |
第一の銅薄膜５１は、例えば、真空雰囲気中に酸素ガスを供給しながら銅ターゲットをスパッタリングして成膜されており、膜中には酸化第一銅（Ｃｕ2Ｏ）、酸化第二銅（ＣｕＯ）等の銅酸化物を含有している。
第二の銅薄膜５２は、例えば、酸素ガスを排気した真空雰囲気で、酸素ガスを供給せずに、銅ターゲットをスパッタリングして成膜されており、膜中には銅酸化物が無いか、あったとしても第一の銅薄膜５１に比べ含有量が少ない。
The first copper
For example, the second copper
第一、第二の銅薄膜５１、５２の積層膜５０をエッチングする工程について説明すると、第二の銅薄膜５２の表面に、所定形状の開口が形成されたレジスト層を配置し、開口底面に第二の銅薄膜５２の表面を露出させる。
The step of etching the laminated
硝酸を含む水溶液に、燐酸と、塩酸とを加え、本発明のエッチング液を作成し、該エッチング液にレジスト層が配置された状態の処理対象基板１０を浸漬させるか、該エッチング液をレジスト層に向けて噴霧して、レジスト層の開口底面に露出する第二の銅薄膜５２にエッチング液を接触させると、第一、第二の銅薄膜５１、５２のうち、レジスト層で覆われた部分はエッチング液に溶解しないが、開口底面に位置する部分はエッチング液に溶解して除去される。
Phosphoric acid and hydrochloric acid are added to an aqueous solution containing nitric acid to prepare the etching solution of the present invention, and the
本発明のエッチング液は、第一、第二の銅薄膜５１、５２をエッチングする速度が変わらないので、第一の銅薄膜５１はオーバーエッチングされずに、レジスト層で覆われた部分が残り、残った第一、第二の銅薄膜５１、５２で、ゲート電極１５や蓄積容量電極１２のような電極膜が形成される（図１（ｂ））。
Since the etching solution of the present invention does not change the etching rate of the first and second copper
ゲート電極１５と蓄積容量電極１２の、ガラス基板１１と密着する側の面には酸を含有する第一の銅薄膜５１が配置されているから、ゲート電極１５と蓄積容量電極１２はガラス基板１１に対する密着性が高い。
ゲート電極１５と蓄積容量電極１２は、第一の銅薄膜５１の他に、酸素を含有しない第二の銅薄膜５２を有しているから、抵抗値が小さい。
Since the first copper
Since the
図１（ｂ）はゲート電極１５と蓄積容量電極１２を形成後、レジスト層を剥離した状態を示している。
図１（ｃ）の符号２０は図１（ｂ）のゲート電極１５と、ゲート絶縁膜１４と、チャネル半導体層１６と、ソース及びドレイン半導体層２５、２６と、ソース及びドレイン電極２１、２２とを有する薄膜トランジスタを示している。
FIG. 1B shows a state where the resist layer is peeled after the
ここでは、チャネル半導体層１６は、ソース及びドレイン半導体層２５、２６と同じ導電型であるが、不純物濃度が低くなっており、ゲート電極１５に電圧を印加すると、チャネル半導体層１６のゲート絶縁膜１４を介してゲート電極１５と接触する部分に低抵抗な蓄積層が形成され、該蓄積層を介してソース半導体層２５とドレイン半導体層２６が電気的に接続される。
Here, the
チャネル半導体層１６は、ソース及びドレイン半導体層２５、２６と反対の導電型であってもよく、この場合、ゲート電極１５に電圧を印加すると、チャネル半導体層１６のゲート絶縁膜１４を介してゲート電極１５と接触する部分に、ソース及びドレイン半導体層２５、２６と同じ導電型の反転層が形成され、該反転層によってソース半導体層２５とドレイン半導体層２６とが電気的に接続される。
なお、図１（ｃ）は薄膜トランジスタ２０が形成された処理対象基板１０の表面に、層間絶縁膜２４と、画素電極２７が形成された状態を示している。
The
FIG. 1C shows a state in which an
画素電極２７はドレイン電極２２に接続されており、ソース半導体層２５とドレイン半導体層２６とを電気的に接続すると、ソース電極２１からドレイン電極２２に電流が流れ、画素電極２７に電圧が印加される。
The
図２の符号４は、画素電極２７上に液晶４１を配置し、ガラス基板４２の表面に対向電極４５が形成されたパネル４０を、対向電極４５が画素電極２７の真上に位置するように配置した液晶表示装置を示しており、画素電極２７と対向電極４５に印加する電圧を制御し、液晶４１の光透過率を制御することができる。
＜比較例１＞
硫酸（Ｈ2ＳＯ4）を２０容量％、硝酸（ＨＮＯ3）を１０容量％、酢酸（ＣＨ3ＣＯＯＨ）を３０容量％、水（Ｈ2Ｏ）を４０容量％含有する水溶液を比較例１のエッチング液とした。即ち、比較例１のエッチング液の組成は、硫酸１０容量部、硝酸５容量部、酢酸１５容量部、水２０容量部である。
<Comparative Example 1>
Comparative Example 1 An aqueous solution containing 20% by volume of sulfuric acid (H 2 SO 4 ), 10% by volume of nitric acid (HNO 3 ), 30% by volume of acetic acid (CH 3 COOH), and 40% by volume of water (H 2 O) Etching solution. That is, the composition of the etching solution of Comparative Example 1 is 10 parts by volume of sulfuric acid, 5 parts by volume of nitric acid, 15 parts by volume of acetic acid, and 20 parts by volume of water.
＜実施例１＞
比較例１のエッチング液に、燐酸濃度８５容量％の燐酸水溶液１．２５ｍｌと、塩酸濃度３５容量％の塩酸水溶液５ｍｌを加え、実施例１のエッチング液を作成した。即ち、実施例１のエッチング液の組成は、硫酸１０容量部、硝酸５容量部、酢酸部１５容量部、燐酸１．０６２５容量部、塩酸１．７５容量部、水２３．４３７５容量部である。
<Example 1>
To the etching solution of Comparative Example 1, 1.25 ml of a phosphoric acid aqueous solution having a phosphoric acid concentration of 85% by volume and 5 ml of a hydrochloric acid aqueous solution having a hydrochloric acid concentration of 35% by volume were added to prepare the etching solution of Example 1. That is, the composition of the etching solution of Example 1 is 10 parts by volume of sulfuric acid, 5 parts by volume of nitric acid, 15 parts by volume of acetic acid, 1.0625 parts by volume of phosphoric acid, 1.75 parts by volume of hydrochloric acid, and 23.4375 parts by volume of water. .
＜実施例２＞
上記実施例１のエッチング液に、更に水を５ｍｌ加えて実施例２のエッチング液を作成した。即ち、実施例２のエッチング液の組成は、硫酸１０容量部、硝酸５容量部、酢酸部１５容量部、燐酸１．０６２５容量部、塩酸１．７５容量部、水２８．４３７５容量部である。
<Example 2>
An etching solution of Example 2 was prepared by adding 5 ml of water to the etching solution of Example 1 above. That is, the composition of the etching solution of Example 2 is 10 parts by volume of sulfuric acid, 5 parts by volume of nitric acid, 15 parts by volume of acetic acid, 1.0625 parts by volume of phosphoric acid, 1.75 parts by volume of hydrochloric acid, and 28.4375 parts by volume of water. .
比較例１と実施例１、２の各エッチング液に、膜厚３００ｎｍの純銅薄膜と、膜厚３００ｎｍの銅酸化物（ＣｕＯ、Ｃｕ2Ｏを含む）薄膜を浸漬し、液温２０℃、４０℃の条件で、それぞれエッチング速度を求めた。 A 300-nm-thick pure copper thin film and a 300-nm-thick copper oxide (including CuO, Cu 2 O) thin film are immersed in the etching solutions of Comparative Example 1 and Examples 1 and 2, and the liquid temperature is 20 ° C., 40 The etching rate was determined under the condition of ° C.
図３〜５は比較例１、実施例１、２のエッチング液の液温と、エッチング速度の関係をグラフ化したものである。図３を見ると、比較例１のエッチング液を用いた場合には、銅酸化物薄膜と純銅薄膜のエッチング速度に差があり、エッチング液の温度を４０℃と高くしてエッチング速度を速めた場合には、銅酸化物薄膜のエッチング速度が純銅薄膜の約１．５倍にもなった。
これに対し、図４、５を見ると、実施例１、２のエッチング液を用いた場合には、液温２０℃ではエッチング速度に差が無くなった。
3 to 5 are graphs showing the relationship between the etching temperature and the etching rate of Comparative Example 1 and Examples 1 and 2. FIG. Referring to FIG. 3, when the etching solution of Comparative Example 1 was used, there was a difference in the etching rate between the copper oxide thin film and the pure copper thin film, and the etching rate was increased to 40 ° C. to increase the etching rate. In some cases, the etching rate of the copper oxide thin film was about 1.5 times that of the pure copper thin film.
On the other hand, in FIGS. 4 and 5, when the etching solutions of Examples 1 and 2 were used, there was no difference in the etching rate at a liquid temperature of 20 ° C.
液温４０℃の場合、実施例１は銅酸化物薄膜のエッチング速度が純銅薄膜のエッチング速度の１．２倍程度まで低下した。実施例２は逆に純銅薄膜の方が銅酸化物薄膜よりも遅くなった。いずれの場合も、液温４０℃でのエッチング速度の差は比較例１よりも小さく、本発明のエッチング液は銅酸化物のエッチング速度が、純銅のエッチング速度に対して遅くすることが分かった。 In the case of a liquid temperature of 40 ° C., in Example 1, the etching rate of the copper oxide thin film decreased to about 1.2 times the etching rate of the pure copper thin film. In contrast, in Example 2, the pure copper thin film was slower than the copper oxide thin film. In either case, the difference in the etching rate at a liquid temperature of 40 ° C. was smaller than that in Comparative Example 1, and it was found that the etching rate of the copper oxide in the etching solution of the present invention was slower than the etching rate of pure copper. .
また、比較例１のエッチング液では、液温２０℃の場合も４０℃の場合も、銅酸化物膜は割れながらエッチングされる傾向があるのに対し、実施例１のエッチング液は、液温４０℃で銅酸化物薄膜をエッチングする際の割れが比較例１に比べて少なく、実施例２のエッチング液は、液温４０℃で銅酸化物薄膜をエッチングする際に割れが確認されなかった。 Moreover, in the etching liquid of Comparative Example 1, the copper oxide film tends to be etched while being cracked at both the liquid temperature of 20 ° C. and 40 ° C., whereas the etching liquid of Example 1 has a liquid temperature. There were few cracks when etching a copper oxide thin film at 40 ° C. compared to Comparative Example 1, and the etching liquid of Example 2 was not confirmed when etching the copper oxide thin film at a liquid temperature of 40 ° C. .
以上のことから、本発明のエッチング液は、銅酸化物の含有量の異なる銅薄膜のエッチング速度の差が小さく、しかも、エッチング中に銅酸化物薄膜の割れが少ないことが確認された。 From the above, it was confirmed that the etching solution of the present invention has a small etching rate difference between copper thin films having different copper oxide contents, and that the copper oxide thin film has few cracks during etching.
１１……ガラス基板 １５……ゲート電極 １４……ゲート絶縁膜 １６……チャネル半導体層 ２１……ソース電極 ２２……ドレイン電極 ２５……ソース半導体層 ２６……ドレイン半導体層 ５０……積層膜 ５１……第一の銅薄膜 ５２……第二の銅薄膜
DESCRIPTION OF
Claims (2)
前記第一の銅薄膜よりも前記銅酸化物の含有量が少ない第二の銅薄膜とが積層された積層膜のエッチングに用いるエッチング液であって、
硫酸と、硝酸と、酢酸と、塩酸と、燐酸とを含有する水溶液で構成されたエッチング液。 A first copper thin film containing copper oxide;
An etching solution used for etching a laminated film in which the second copper thin film having a lower copper oxide content than the first copper thin film is laminated,
An etching solution composed of an aqueous solution containing sulfuric acid, nitric acid, acetic acid, hydrochloric acid, and phosphoric acid.
前記ゲート電極は、ガラス基板の表面に密着する第一の銅薄膜と、前記第一の銅薄膜の表面に配置され、前記第一の銅薄膜よりも銅酸化物の含有量が少なくされた第二の銅薄膜とからなる積層膜を、パターニングして形成された薄膜トランジスタを製造する薄膜トランジスタ製造方法であって、
前記積層膜の前記第二の銅薄膜の表面に、所定形状の開口が形成されたレジスト層を配置し、
前記開口の底面に露出する前記積層膜に、硫酸と、硝酸と、酢酸と、燐酸と、塩酸とを含有する水溶液からなるエッチング液を接触させて前記積層膜をパターニングするトランジスタ製造方法。 A gate electrode, a gate insulating film, a channel semiconductor layer, a drain semiconductor layer, and a source semiconductor layer;
The gate electrode is disposed on the surface of the first copper thin film and the first copper thin film in close contact with the surface of the glass substrate, and the content of copper oxide is less than that of the first copper thin film. A thin film transistor manufacturing method for manufacturing a thin film transistor formed by patterning a laminated film composed of two copper thin films,
On the surface of the second copper thin film of the laminated film, a resist layer in which an opening having a predetermined shape is formed,
A method of manufacturing a transistor, comprising: patterning the laminated film by bringing an etching solution made of an aqueous solution containing sulfuric acid, nitric acid, acetic acid, phosphoric acid, and hydrochloric acid into contact with the laminated film exposed on a bottom surface of the opening.
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