CN113802120A - Acidic titanium-tungsten etching solution for semiconductor - Google Patents
Acidic titanium-tungsten etching solution for semiconductor Download PDFInfo
- Publication number
- CN113802120A CN113802120A CN202111084450.XA CN202111084450A CN113802120A CN 113802120 A CN113802120 A CN 113802120A CN 202111084450 A CN202111084450 A CN 202111084450A CN 113802120 A CN113802120 A CN 113802120A
- Authority
- CN
- China
- Prior art keywords
- titanium
- acid
- tungsten
- etching
- etching solution
- 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.)
- Withdrawn
Links
- 238000005530 etching Methods 0.000 title claims abstract description 35
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000004065 semiconductor Substances 0.000 title claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000012190 activator Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical group OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 abstract description 11
- 239000010937 tungsten Substances 0.000 abstract description 11
- 229910001080 W alloy Inorganic materials 0.000 abstract description 9
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
Abstract
The invention belongs to the technical field of metal etching, and particularly relates to an acidic titanium-tungsten etching solution for a semiconductor, which comprises the following components in percentage by mass: 50-70 wt% of phosphoric acid, 5-10 wt% of strong oxidizing acid, 5-10 wt% of surface active component, 1-5 wt% of titanium activator and the balance of deionized water. According to the invention, the titanium activator is added into the formula, so that the etching efficiency is higher, the selection ratio of titanium nitride to metal tungsten can be controlled, and the synchronous etching requirement of customers on the titanium-tungsten alloy can be better met.
Description
Technical Field
The invention relates to the technical field of metal etching, in particular to an acidic titanium-tungsten etching solution for a semiconductor.
Background
Titanium tungsten alloys are commonly used as materials for auxiliary thin film metallization in semiconductor related manufacturing because of their excellent corrosion resistance and strong adhesion to various thin film layers. The titanium-tungsten alloy is actually a coating with a two-layer structure of titanium nitride and metal tungsten, and the titanium nitride is more inert than the metal tungsten and is generally positioned on the outer layer of the metal tungsten.
In the prior art, hydrogen peroxide or normal periodic acid is generally used for etching titanium-tungsten alloy. But the peroxide has poor stability and is unsafe. And the two reagents cannot give consideration to the etching rate and the selectivity ratio between titanium nitride and metal tungsten of the titanium-tungsten alloy, because the metal tungsten can suppress etching liquid to etch the titanium nitride, and if the selectivity ratio of the titanium nitride is balanced, the etching rate of the metal tungsten is sacrificed, so that the high-precision processing requirement of semiconductor manufacturing cannot be met.
Therefore, the present invention provides a new etching solution formula to solve the above problems.
Disclosure of Invention
The invention mainly aims to provide an acidic titanium-tungsten etching solution for a semiconductor, which can control the etching efficiency of two components of a titanium-tungsten alloy through a titanium activator so that the two components can be etched synchronously.
The invention realizes the purpose through the following technical scheme: an acid titanium tungsten etching solution for a semiconductor comprises the following components in percentage by mass: 50-70 wt% of phosphoric acid, 5-10 wt% of strong oxidizing acid, 5-10 wt% of surface active component, 1-5 wt% of titanium activator and the balance of deionized water.
Specifically, the strong oxidizing acid is preferably nitric acid.
Specifically, the surface active ingredient is preferably acetic acid.
The acid titanium tungsten etching solution for the semiconductor has the beneficial effects that:
according to the invention, the titanium activator is added into the formula, so that the etching efficiency is higher, the selection ratio of titanium nitride to metal tungsten can be controlled, and the synchronous etching requirement of customers on the titanium-tungsten alloy can be better met.
Detailed Description
An acid titanium tungsten etching solution for a semiconductor comprises the following components in percentage by mass: 50-70 wt% of phosphoric acid, 5-10 wt% of strong oxidizing acid, 5-10 wt% of surface active component, 1-5 wt% of titanium activator and the balance of deionized water.
Since both titanium nitride and metallic tungsten are inert, the etching reaction needs to be accomplished by a strong oxidizing acid. Nitric acid is preferred as the strongly oxidizing acid because it is inexpensive, simple and readily available.
The surface active component is used for helping the etching solution to soak the surface of the titanium-tungsten alloy, so that the etching efficiency is improved. Compared with the common surfactant, the acetic acid is more suitable for the acidic solution environment, and the acetic acid has low cost and is simple and easy to obtain.
In the invention, besides the etching effect is ensured by adopting the conventional phosphoric acid, nitric acid and acetic acid, the titanium can be activated by using the nitrilotriacetic acid, so that the selectivity of the etching solution to the titanium nitride is improved, and the etching rate of the etching solution to the titanium nitride is improved.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Examples 1 to 5:
the acidic TiW etchants for semiconductors of examples 1-5 were prepared by mixing the formulations of Table 1:
table 1: unit: wt.%
Note: the part of the content less than 100 wt% is made up by deionized water to make up the balance.
A comparative experiment was conducted with the etchants of examples 1 to 5 using 50 wt% hydrogen peroxide as control 1 and positive periodic acid as control 2. Experimental method seven 1cm × 1cm substrates plated with 1000nm of metal tungsten and 1000nm of titanium nitride were prepared, immersed in a sufficient amount of the etching solutions of examples 1-5 and comparative examples 1-2 at normal temperature for 1 hour, respectively, and then the etching efficiency per minute was calculated from the change in the average thickness, with the results shown in Table 2.
Table 2:
as can be seen from table 2, the etching solutions of examples 1 to 5 have relatively high etching efficiency compared to comparative examples 1 to 2, and the selection ratio of titanium nitride to metal tungsten is controlled to be 1:1, so that the requirement of customers on the synchronous etching of titanium-tungsten alloy can be better satisfied.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (4)
1. An acid titanium tungsten etching solution for a semiconductor is characterized by comprising the following components in percentage by mass: 50-70 wt% of phosphoric acid, 5-10 wt% of strong oxidizing acid, 5-10 wt% of surface active component, 1-5 wt% of titanium activator and the balance of deionized water.
2. The acidic TiW etchant for semiconductor according to claim 1, wherein said titanium activator is preferably nitrilotriacetic acid.
3. The acidic titanium-tungsten etching solution for semiconductors according to claim 1, characterized in that: the strongly oxidizing acid is preferably nitric acid.
4. The acidic titanium-tungsten etching solution for semiconductors according to claim 1, characterized in that: the surface active ingredient is preferably acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111084450.XA CN113802120A (en) | 2021-09-16 | 2021-09-16 | Acidic titanium-tungsten etching solution for semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111084450.XA CN113802120A (en) | 2021-09-16 | 2021-09-16 | Acidic titanium-tungsten etching solution for semiconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113802120A true CN113802120A (en) | 2021-12-17 |
Family
ID=78895476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111084450.XA Withdrawn CN113802120A (en) | 2021-09-16 | 2021-09-16 | Acidic titanium-tungsten etching solution for semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113802120A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110195229A (en) * | 2019-06-21 | 2019-09-03 | 湖北兴福电子材料有限公司 | A kind of etching solution and its application method of tungsten and titanium nitride metal film |
| CN112080279A (en) * | 2019-06-12 | 2020-12-15 | 关东鑫林科技股份有限公司 | Etching composition |
-
2021
- 2021-09-16 CN CN202111084450.XA patent/CN113802120A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112080279A (en) * | 2019-06-12 | 2020-12-15 | 关东鑫林科技股份有限公司 | Etching composition |
| CN110195229A (en) * | 2019-06-21 | 2019-09-03 | 湖北兴福电子材料有限公司 | A kind of etching solution and its application method of tungsten and titanium nitride metal film |
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| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211217 |