JPS59171126A - Etchant for palladium - Google Patents
Etchant for palladiumInfo
- Publication number
- JPS59171126A JPS59171126A JP4423583A JP4423583A JPS59171126A JP S59171126 A JPS59171126 A JP S59171126A JP 4423583 A JP4423583 A JP 4423583A JP 4423583 A JP4423583 A JP 4423583A JP S59171126 A JPS59171126 A JP S59171126A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- film
- iodine
- ammonium iodide
- aperture
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 47
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 21
- 238000005530 etching Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052740 iodine Inorganic materials 0.000 abstract description 21
- 239000011630 iodine Substances 0.000 abstract description 21
- 229910021332 silicide Inorganic materials 0.000 abstract description 21
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001080 W alloy Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000005468 ion implantation Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000001259 photo etching Methods 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
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- -1 sodium Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
【発明の詳細な説明】 〔発明の利用分野〕 本発明はパラジウムのエツチング液に関する。[Detailed description of the invention] [Field of application of the invention] The present invention relates to a palladium etching solution.
し背景技術〕
従来、シリコン半導体装置のケイ化パラジウム電極の製
造においては、上衣面が絶縁膜で覆われたシリコン半導
体基体−Ｈに、−削孔を開［」シリコン半導体衣而を露
出させた後、パラジウムを蒸着し、さらに熱処理を行な
い、上記開孔部にのみケイ化パラジウムを形成し、未反
応のパラジウムのみをヨウ化カリウム、およびヨウ素の
混合水溶液で除去することにより形成した。ヨウ化カリ
ウム、およびヨウ素の水溶液は、パラジウムをエツチン
グするが、ケイ化パラジウムをほとんどエツチングしな
いため、上記開孔部にのみ選択ｔ″１・ｊにケイ化パラ
ジウムを形成することができた。BACKGROUND TECHNOLOGY Conventionally, in the production of palladium silicide electrodes for silicon semiconductor devices, a hole is drilled in a silicon semiconductor substrate H whose upper surface is covered with an insulating film to expose the silicon semiconductor substrate. Thereafter, palladium was vapor-deposited and further heat-treated to form palladium silicide only in the openings, and only unreacted palladium was removed with a mixed aqueous solution of potassium iodide and iodine. An aqueous solution of potassium iodide and iodine etches palladium, but hardly etches palladium silicide, so palladium silicide could be formed only in the openings at the selected t″1·j.
しかし、ヨウ化カリウム、およびヨウ素の水溶液には、
カリウムが含まれる。寸だ、ヨウ化カリウムには一般（
で、ナトリウムが不純物として多ｈ１に含捷れる。ナト
リウム、カリウム等のアルカリ金属は、シリコン半導体
装置に広く用いられる酸化シリコン膜中の拡散が極めて
早く、また、イオン化し易い。このように、イオン化し
たアルカリ金属は、シリコン半導体の表面電位を変動さ
せる。However, aqueous solutions of potassium iodide and iodine have
Contains potassium. In fact, potassium iodide has a common (
Sodium is included as an impurity in the polyh1. Alkali metals such as sodium and potassium diffuse extremely quickly in silicon oxide films widely used in silicon semiconductor devices, and are easily ionized. In this way, the ionized alkali metal changes the surface potential of the silicon semiconductor.
シリコン半導体の表面電位の変動は、ＭＯＳダイオード
のしきい値電圧変動等、シリコン半導体装置の特性不良
を引き起こす。このため、ヨウ化カリウム、およびヨウ
素の混合水溶液をケイ化パラジウム電極の作製に用いる
のは望ましくない。Fluctuations in the surface potential of silicon semiconductors cause characteristic defects in silicon semiconductor devices, such as fluctuations in the threshold voltage of MOS diodes. For this reason, it is not desirable to use a mixed aqueous solution of potassium iodide and iodine for producing a palladium silicide electrode.
本発明の目的は、シリコン半導体装置のケイ化パラジウ
ム電極の製造法において、アルカリ金属を含−まないパ
ラジウムとケイ化パラジウムの選択エツチング液を提供
することである。An object of the present invention is to provide a selective etching solution for palladium and palladium silicide that does not contain an alkali metal in a method for manufacturing palladium silicide electrodes for silicon semiconductor devices.
本発明は、ヨウ化カリウムを使用することなしに、ヨウ
化アンモニウムを使用するものである。The present invention uses ammonium iodide without using potassium iodide.
ヨウ化カリウムはカリウムを含むが、さらにカリウムと
同族同素であるナトリウム等のアルカリ金属を不純物と
して含む。先に述べたように、アルカリ金属は、シリコ
ン半導体装置の特性不良の原因となる。一方、ヨウ化ア
ンモニウムはアルカリ金属をほとんど含壕ない。このた
め、シリコン半導体装置製造工程中に本発明によるパラ
ジウムのエツチング液を使用しても、シリコン半導体装
省の特性不良を引き起こすことはない。Potassium iodide contains potassium, but it also contains impurities such as alkali metals such as sodium, which are homologous to potassium. As mentioned above, alkali metals cause poor characteristics of silicon semiconductor devices. On the other hand, ammonium iodide contains almost no alkali metal. Therefore, even if the palladium etching solution according to the present invention is used during the manufacturing process of silicon semiconductor devices, it will not cause defects in the characteristics of the silicon semiconductor devices.
以下、ケイ化パラジウム電極を用いたｐ −ｎダイオー
ドの製造法に関する実施例を用いて、本発明の詳細な説
明する。Hereinafter, the present invention will be described in detail using an example of a method for manufacturing a p-n diode using a palladium silicide electrode.
まず、第１図に示すように、ｐ型半導体基鈑に通常の拡
散法、およびイオン注入法によりｎ型領域２を形成１７
、その後、熱酸化により、酸化シリコン膜３を形成した
。さらに、通常写真食刻法により、孔４を酸化／リコン
膜３に開口した。次に通常の蒸滑法によりパラジウム膜
５を形成した。First, as shown in FIG. 1, an n-type region 2 is formed 17 on a p-type semiconductor substrate by a normal diffusion method and an ion implantation method.
Then, a silicon oxide film 3 was formed by thermal oxidation. Further, holes 4 were opened in the oxidation/recon film 3 by ordinary photolithography. Next, a palladium film 5 was formed by a normal evaporation method.
さらに、第２図に示すように、１５０Ｕ以十の熱処理を
行ないパラジウム膜５とＩ］型シリコン基板２とを反応
させることにより、孔４の近傍にケイ化パラジウム層６
を形成した。その後、第３図に示すように、ヨウ化アン
モニウムおよびヨウ素の混合水溶液により、未反応のパ
ラジウム膜５を除去した。このとき、ヨウ化アンモニウ
ムおよびヨウ素の混合水溶液の濃度を重量比で、ヨウ化
アンモニウム４ Ｗ １％以上、ヨウ素０．０］、ｗｔ
％以にとすると、同液によるパラジウムのエツチング速
度は、ケイ化パラジウムのエツチング速度（Ｄ １０倍
以上である匁第、ケン化パラジウム層６は、未反応パラ
ジウム膜５のエツチング後も、存在することから、ケイ
化パラジウム電極が形成できた。Further, as shown in FIG. 2, a heat treatment of 150 U or more is performed to react the palladium film 5 and the I type silicon substrate 2, thereby forming a palladium silicide layer 6 in the vicinity of the hole 4.
was formed. Thereafter, as shown in FIG. 3, the unreacted palladium film 5 was removed using a mixed aqueous solution of ammonium iodide and iodine. At this time, the concentration of the mixed aqueous solution of ammonium iodide and iodine was determined by weight ratio: ammonium iodide 4W 1% or more, iodine 0.0], wt
%, the etching rate of palladium by the same solution is at least 10 times the etching rate of palladium silicide (D), and the saponified palladium layer 6 remains even after the unreacted palladium film 5 is etched. Therefore, a palladium silicide electrode could be formed.
さらに、チタンおよびタングステンの合金膜７、アルミ
ニウム膜８を順次通常の蒸五法で形成し、さらに、通常
の写真食刻法でアルミニウム膜８、チタンおよびタング
ステンの合金膜７を順次エツチングし、配線層を形成し
た。Furthermore, a titanium and tungsten alloy film 7 and an aluminum film 8 are sequentially formed using a normal vapor deposition method, and further, the aluminum film 8 and a titanium and tungsten alloy film 7 are sequentially etched using a normal photolithography method to form wiring lines. formed a layer.
次に、ヨウ化アンモニウムおよびヨウ素の混合水溶液に
よるパラジウムのエチング速度を第４図および第５図に
示す。Next, the etching rate of palladium by a mixed aqueous solution of ammonium iodide and iodine is shown in FIGS. 4 and 5.
第４図はヨウ化アンモニウムおよびヨウ素混合水ｍ 液
（７Ｊ）ヨウ素濃度によるパラジウムのエツチング速度
依存性を示したものである。なお、ヨウ化アンモニウム
と水との重量比は０．５で、測定温度は２５Ｃ１である
。第４図より、ヨウ素濃度が重量比でｏ、ｏｉｗｔ％以
上であれば、パラジウムのエツチング速度は１５ｎｍ／
ｍｉｎ以上である。寸だ、ヨウ化アンモニウムおよびヨ
ウ素の混合水溶液によるケイ化パラジウムのエツチング
速度は約１〜１、５ ｎｍ／ｍ ｉ ｎ程度である。従
って、ヨウ素濃度が０．０１ｗ１３以上であれば、ケイ
化パラジウムとパラジウムのエッチング速度比１ｔｌｏ
倍以上となり、パラジウムのみを選択的にエツチングし
、ケイ化パラジウムのみを残すことができる。FIG. 4 shows the dependence of palladium etching rate on the iodine concentration of ammonium iodide and iodine mixed water solution (7 J). Note that the weight ratio of ammonium iodide to water was 0.5, and the measurement temperature was 25C1. From Fig. 4, if the iodine concentration is 0, oiwt% or more by weight, the etching rate of palladium is 15 nm/
It is more than min. In fact, the etching rate of palladium silicide with a mixed aqueous solution of ammonium iodide and iodine is about 1 to 1.5 nm/min. Therefore, if the iodine concentration is 0.01w13 or more, the etching rate ratio of palladium silicide and palladium is 1tlo.
This makes it possible to selectively etch only palladium, leaving only palladium silicide.
第５図はヨウ化アンモニウムおよびヨウ素混合化溶液の
ヨウ化アンモニウム濃度によるパラジウムのエツチング
速度依存性を示したものである。FIG. 5 shows the dependence of the palladium etching rate on the ammonium iodide concentration of the ammonium iodide and iodine mixed solution.
なお、ヨウ素とヨウ化アンモニウムの重量比−０，１で
あり、測定温度は２５Ｃである。第５図よシ、ヨウ化ア
ンモニウム濃度が重量比で４Ｗｊ％以上あれば、パラジ
ウムのエツチング速度け１５ｎｍ／ｍｉｎ以上である。Note that the weight ratio of iodine and ammonium iodide is -0.1, and the measurement temperature is 25C. As shown in FIG. 5, when the ammonium iodide concentration is 4 Wj% or more by weight, the palladium etching rate is 15 nm/min or more.
捷だ、ヨウ化アンモニウムおよびヨウ素の混合水溶液に
よるケイ化パラジウムのエツチング速度は１〜１．５
ｎｍ／ｍ ｉ ｎ 程度である。従って、ヨウ化アン
モニウム濃度が４ｗｔ％以上あれば、ケイ化パラジウム
とパラジウムのエツチング速度比は１０倍以上であり、
パラジウムのみを選択的にエツチングでき、ケイ化パラ
ジウムのみを残すことができる。However, the etching rate of palladium silicide with a mixed aqueous solution of ammonium iodide and iodine is 1 to 1.5.
It is about nm/min. Therefore, if the ammonium iodide concentration is 4 wt% or more, the etching rate ratio of palladium silicide and palladium is 10 times or more,
Only palladium can be selectively etched, leaving only palladium silicide.
第４図、および第５図の結果から、重匍゛化において、
ヨウ素濃度が０．０１ｗ１３以上で、かつ、ヨウ化アン
モニウムが４ｗｔ％以上であれば、ヨウ化アンモニウム
およびヨウ素の混合水溶液で、１０倍以上の選択比で、
パラジウムをエツチングし、ケイ化パラジウムを残すこ
とができる。From the results shown in Figures 4 and 5, in increasing weight,
If the iodine concentration is 0.01w13 or more and the ammonium iodide is 4wt% or more, a mixed aqueous solution of ammonium iodide and iodine with a selectivity of 10 times or more,
Palladium can be etched leaving behind palladium silicide.
第１図乃至第３図は本発明の一実施例を示す工程図、第
４図および第５図は本発明の効果を示す曲線図である。
１．２・・・シリコン半導体基板、３・・・酸化シリコ
ン膜、４・・・孔、５・・・パラジウム膜、６・・・ケ
イ化パラジウム層、７・・・チタンおよびタングステン
の合金■ １ 図
第 ／ ｎ
千 ３ 図
第 ４ し１
！−一、 −一−−，１
１（ＩＩ 、、−、、−２□。ｔｕｔｙ） ”’ “
′佑 ５ 図
、ＮＨａＩ湾屓 （−ｂｉｔ別FIGS. 1 to 3 are process diagrams showing one embodiment of the present invention, and FIGS. 4 and 5 are curve diagrams showing the effects of the present invention. 1.2... Silicon semiconductor substrate, 3... Silicon oxide film, 4... Hole, 5... Palladium film, 6... Palladium silicide layer, 7... Titanium and tungsten alloy ■ 1 Figure No./n 1,000 3 Figure 4 Shi 1! -1, -1--,1 1(II,,-,,-2□.tuty) ”' “
'Yu 5 Figure, NHaI bay (-by bit)
Claims (1)
、ヨウ素はぼ０．０１ｗｔ％以上、残部水から成るパラ
ジウムのエツチング液。A palladium etching solution consisting of approximately 4 wt% or more of ammonium iodide, approximately 0.01 wt% or more of iodine, and the balance water in terms of weight ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4423583A JPS59171126A (en) | 1983-03-18 | 1983-03-18 | Etchant for palladium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4423583A JPS59171126A (en) | 1983-03-18 | 1983-03-18 | Etchant for palladium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59171126A true JPS59171126A (en) | 1984-09-27 |
Family
ID=12685865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4423583A Pending JPS59171126A (en) | 1983-03-18 | 1983-03-18 | Etchant for palladium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59171126A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7265040B2 (en) * | 2002-12-05 | 2007-09-04 | Samsung Electronics Co., Ltd. | Cleaning solution and method for selectively removing layer in a silicidation process |
-
1983
- 1983-03-18 JP JP4423583A patent/JPS59171126A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7265040B2 (en) * | 2002-12-05 | 2007-09-04 | Samsung Electronics Co., Ltd. | Cleaning solution and method for selectively removing layer in a silicidation process |
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