CN104375394A - Etching liquor and mask plate forming method - Google Patents
Etching liquor and mask plate forming method Download PDFInfo
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- CN104375394A CN104375394A CN201410650611.0A CN201410650611A CN104375394A CN 104375394 A CN104375394 A CN 104375394A CN 201410650611 A CN201410650611 A CN 201410650611A CN 104375394 A CN104375394 A CN 104375394A
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- etching
- etching solution
- perchloric acid
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Abstract
The invention relates to an etching liquor and a mask plate forming method. The etching liquor comprises perchloric acid, ceric ammonium nitrate and water in a proportion of 500mL to (2Kg-3Kg) to (12L-16L). The mask forming method comprises photoetching, developing, etching and demolding, wherein the etching is performed by using the etching liquor. The etching liquor adopts the perchloric acid with the relatively low concentration, and the content of the ceric ammonium nitrate is reduced, the amount of volatile gas is reduced from the source, and the relatively heavy odor is avoided; the etching liquor is relatively safe and relatively environmentally-friendly, and the cost is relatively reduced; by adopting the etching liquor with the proportion for etching, etching lines of a plate are good in quality, good in linearity and relatively small in defect number.
Description
Technical field
The present invention relates to etching process techniques field, be specifically related to a kind of etching solution and mask plate formation method.
Background technology
In semiconductor devices makes, light shield is one of conventional instrument.Light shield normally scribes the geometry wiring diagram designed in high-purity quartz or soda glass substrate.Photoetching technique is applied to photaesthesia glue, it is painted on metal substrate or glass surface as one polymerization soluble matters, and then photoresist is baked except desolventizing, then by it by electron beam or laser beam exposure, then chemical process process is carried out, as techniques such as development, etchings.
Early stage etching solution is with the synthesis of cerous nitrate ammonia, glacial acetic acid and water proportioning, mostly adopt now the stoste adding catalytic elements of import, due to simple cerous nitrate ammonia, glacial acetic acid and water proportioning synthesis etching solution and the chromium film reaction time slower, etch uneven, the import stoste reaction time is very fast, and etching evenly.But import stoste is expensive, price is on the market 3.6 liters at present probably needs 200 dollars, can etch about 30, and fancy price like this causes mask plate successive process and drops into very large, considerably increases processing procedure cost.
In addition, existing etching solution in R&D process below difficulty: 1. etching solution volatilization gas (mainly HCl and Cl
2) phenomenon relatively serious, have serious peculiar smell, can working the mischief to environment and processing procedure personnel; 2. etching solution has obvious crystalline polamer after having grown service time, can cause the hidden danger that plate scratches; 3. after etch slide is counted to and reached certain sheet number, in solution, ion concentration is too high, shows as solution colour too dark, is unfavorable for that reaction is carried out.
Summary of the invention
In view of this, the etching solution that a kind of gaseous volatilization is few, cost is low, etch effect is good is provided and applies the mask plate formation method of this etching solution.
A kind of etching solution, it comprises perchloric acid, ammonium ceric nitrate and water, and the proportioning of described perchloric acid, ammonium ceric nitrate and water is 500mL:2Kg-3Kg:12L-16L.
And a kind of mask plate formation method, it comprises photoetching, development, etching and demoulding, and described etching etches plate with etching solution as above.
Above-mentioned etching solution adopts the perchloric acid of low concentration, and the content of ammonium ceric nitrate also reduces, and reduces the gas flow of volatilization from root, does not have heavier peculiar smell to produce, safety and environmental protection more, and cost also reduces a lot relatively.And after adopting the etching solution of said ratio to etch, plate etching line quality is good, and linearly better, defect counts is less, can compare favourably with the effect of the stoste of import.
Accompanying drawing explanation
Fig. 1 is product SEM(scanning electron microscope after the etching solution etching using comparative example configuration) enlargement factor of figure, this figure is 10,000 times.
Fig. 2 is that after the etching solution etching using embodiment 1 to configure, product SEM schemes, and the enlargement factor of this figure is 10,000 times.
Fig. 3 is that after the etching solution etching using embodiment 2 to configure, product SEM schemes, and the enlargement factor of this figure is 10,000 times.
Fig. 4 is that after the etching solution etching using embodiment 3 to configure, product SEM schemes, and the enlargement factor of this figure is 10,000 times.
Fig. 5 is that after the etching solution etching using embodiment 4 to configure, product SEM schemes, and the enlargement factor of this figure is 10,000 times.
Fig. 6 is that after using the etching solution etching of comparative example configuration, the SEM of the lower multiple of product schemes, and the enlargement factor of this figure is 5,000 times.
Fig. 7 and Fig. 8 is the rear product surface microphoto of etching solution etching using comparative example configuration, and the enlargement factor of this figure is 1,000 times.
Embodiment
Below with reference to specific embodiment, the present invention is described in detail.
The etching solution of the embodiment of the present invention, by reducing the concentration of perchloric acid, ammonium ceric nitrate, reduces gaseous volatilization, and desalination peculiar smell, reduce costs, the effect after etching is better.This etching solution comprises perchloric acid, ammonium ceric nitrate and water, and the proportioning of described perchloric acid, ammonium ceric nitrate and water is 500mL:2Kg-3Kg:12L-16L.
The present embodiment reduces perchloric acid, the concentration of ammonium ceric nitrate mainly draws by studying the reaction mechanism in etching process and test.For chromium plate, etching solution is chromium plate etching solution.From reaction mechanism, in etching process, Cr finally can become (Cr(NH
3)
xcl
y) Cl
z (1-6)complex, it mainly affects by the ammonium root in solution and chlorine ion concentration, in addition along with the carrying out of reaction also can be subject to the impact of chromium ion concentration.Through primary Calculation, 1000gCe (NH
4)
2(NO
3)
6can react 230 multiple chromium plates (calculate by PZ/AZ1500 7000A 450*550*4.8, ensure that reactant concentration is greater than 50%), along with the chromium plate of etching solution process gets more and more, the biggest obstacle of obstruction reaction is also the concentration of the chromium ion in solution.Find through research experiment, etching solution better dissolve chromium can be enable by the concentration reducing reactant, ensure balanced the carrying out smoothly, to reach the etch effect required for production of reaction, accomplish maximum material utilization rate, and cost-saving when not affecting result of use.
Preferably, the proportioning of described perchloric acid, ammonium ceric nitrate and water is 500mL:2Kg-3Kg:13L-14L.More preferably, the proportioning of ammonium ceric nitrate and water is less than or equal to 2Kg:12L.The volume proportion of perchloric acid and water is less than or equal to 0.112:3.In a preferred embodiment, the proportioning of perchloric acid, ammonium ceric nitrate and water is 22.4mL: 0.1Kg: 0.6L.The water adopted in etching solution is preferably deionized water.Perchloric acid is preferably analyzed pure, and concentration is more than 99%.
The embodiment of the present invention also provides a kind of mask plate formation method, and it comprises photoetching, development, etching and demoulding, and wherein, etching adopts etching solution as above to etch plate.Particularly, the plate of mask plate, for chromium plate, chromium plate is pre-formed mask, and then carries out photoetching, make mask exposure, developed by developing process again, make mask form the good pattern of predetermined design, then etch further with etching solution, with this predetermined design pattern for template, chromium plate etches corresponding pattern, then mask is removed, namely form chromium material mask plate.
In etching process, etching period is preferably 50-70 second, is more preferably 60-64 second.Every 12 liters of etching solutions are changed after etching more than 60 plates.In addition, in mask plate formation method, carry out the steps such as dimensional measurement, defect inspection, repairing and cleaning further after demoulding, after being checked through defect, corresponding defect is repaired, then clean chromium plate, finally stick dust-proof glue again and deposit.
Illustrate that etching solution of the present invention and wherethrough reason form the aspects such as the performance of mask plate and effect below by way of instantiation and comparative example.
Embodiment 1
The deionized water of 400ml is dissolved in 50g ammonium ceric nitrate, then add the perchloric acid of 11ml, be configured to etching solution, carry out polishing by the little version (test plate) of this etching solution to the demoulding completely of 5 inches, observing etching required time elongated, is 54s.Carry out Quality Detection to the chromium plate after the etching of this block again, recording chromium residues quantity is 0.Observe the color of etching solution, smell simultaneously, and the chromium plate outward appearance after etching.The present embodiment adopts the instrument such as SEM and optical microscope (amplifying about 2,000 times) to carry out microscopic observation, and following examples and comparative example herewith, repeat no more.
Embodiment 2
Get 100g ammonium ceric nitrate and 22.4ml perchloric acid, with the dilution of 600ml deionized water, be configured to etching solution, carry out polishing with this etching solution to the plate of 5 inches, etching required time is 64 seconds.Carry out Quality Detection to the chromium plate after the etching of this block again, recording chromium residues quantity is 0.Observe the color of etching solution, smell simultaneously, and the chromium plate outward appearance after etching.
Embodiment 3
Get 500g ammonium ceric nitrate and 125 ml perchloric acid, with 3250 ml deionized waters dilutions, be configured to etching solution, carry out polishing with this etching solution to the plate of 5 inches, etching required time is 70 seconds.Carry out Quality Detection to the chromium plate after the etching of this block again, recording chromium residues quantity is 0.Observe the color of etching solution, smell simultaneously, and the chromium plate outward appearance after etching.
Embodiment 4
Get 1.5Kg ammonium ceric nitrate and 250 ml perchloric acid, with the dilution of 6L deionized water, be configured to etching solution, carry out polishing with this etching solution to the plate of 5 inches, etching required time is 60 seconds.Carry out Quality Detection to the chromium plate after the etching of this block again, recording chromium residues quantity is 0.Observe the color of etching solution, smell simultaneously, and the chromium plate outward appearance after etching.
Comparative example
1000g ammonium ceric nitrate, 224ml perchloric acid, by 4000ml deionized water mixing and stirring, is configured to etching solution, carries out polishing with this etching solution to the plate of 5 inches, and etching required time is 62 seconds.Carry out Quality Detection to the chromium plate after the etching of this block again, recording chromium residues quantity is 0.Observe the color of etching solution, smell simultaneously, and the chromium plate outward appearance after etching.
By the chromium plate after the etching solution process of preparing above-mentioned instantiation, we find, the etching solution color of the present embodiment preparation is closer to import etching solution.And use the etching solution after optimizing, from the quality of test plate, do not have bad feedback, it is embodied in, and line quality is good, and linearly better, defect counts is less.From etch process, the time equalization of etching is all control at about 1min.Compare two beta version treatment effects of embodiment 2 and comparative example, result is as shown in table 1 below.
Table 1
The white defect of the black convex short circuit of project etching period line quality chromium residues
Embodiment 1 54s 0000
Embodiment 2 70s 0000
Embodiment 3 64s 0000
Embodiment 4 60s 0000
Comparative example 62s 0000
Refer to Fig. 1 to 5, show the rear product graphical effect of etching solution etching using comparative example and embodiment 1-4 configuration respectively, from surface topography in figure, chromium plate lines flat smooth after the etching solution etching of embodiment 1-4 configuration, the better effects if of embodiment 1-2, substantially free of impurities in linear slit, and in chromium plate linear slit after the etching solution process of comparative example, impurity is more.Prove thus, the product quality of the etching solution process of embodiment 1-4 configuration is better.Fig. 6 is the outside drawing of the lower multiple of product after the etching solution etching of comparative example, and as seen from the figure, outward appearance lines are better.But the photo display of Fig. 7 and 8, comparative example has chromium residues.
Sheet number test experiments
Carry out demoulding cleaning to the useless version of 30 16*18 inches, then carry out polishing with the etching solution of embodiment 2 proportioning and the etching solution of comparative example, every sheet processes rear observation etching solution outward appearance.Make discovery from observation, two kinds of complete 15 after etching liquid colors of etching solution polishing obviously deepen, but the etching solution of the present embodiment proportioning is much more shallow than the etching solution color of comparative example, then we carry out etching and contrast effect to two pieces of beta versions, and concrete outcome is as following table 2.As seen from table, the etching solution of embodiment 2 is 0 processing 15 after etching liquid chromium residues, and chromium residues appears in comparative example.In addition, do not find to there is crystal in etching bath after process chromium plate after etching liquid leaves standstill several days yet, avoid the hidden danger that plate scratches.
Table 2
| Project | Etching period | Line quality | Chromium residues | Black convex | Short circuit | White defect |
| Embodiment 2 | 70s | Good | 0 | 0 | 0 | 0 |
| Comparative example | 76s | Good | 2 | 0 | 0 | 0 |
From cost, the etching solution of the present embodiment is much lower compared with import etching solution, is specifically compared as follows:
The import etching solution of current use:
(200 U.S. dollar × 6.3) × 3.5 barrels
Import etching solution 12L can etch 30, and import etching solution etches the conventional version (16*18 inch) of a slice and spends 200*6.3*3.5/30=147.
The etching solution of the present embodiment preparation: ammonium ceric nitrate 1300 yuan/KG, perchloric acid 600 yuan/500ml
The etching solution 12L of the present embodiment preparation can etch 60
Import etching solution etches conventional version (16*18 inch) cost of a slice (1300*2.3+300)/60=54 unit
Save etching cost 300%.
Above-mentioned etching solution adopts the perchloric acid of low concentration, and the content of ammonium ceric nitrate also reduces, and reduces the gas flow of volatilization from root, does not have heavier peculiar smell to produce, safety and environmental protection more, and cost also reduces a lot relatively.And after adopting the etching solution of said ratio to etch, plate etching line quality is good, and linearly better, defect counts is less, can compare favourably with the effect of the stoste of import.And, by autogamy etching solution, reduce the danger of the not enough supply shortage of the import etching solution supply of material.
It should be noted that; the present invention is not limited to above-mentioned embodiment, and according to creative spirit of the present invention, those skilled in the art can also make other changes; these changes done according to creative spirit of the present invention, all should be included within the present invention's scope required for protection.
Claims (10)
1. an etching solution, is characterized in that, comprises perchloric acid, ammonium ceric nitrate and water, and the proportioning of described perchloric acid, ammonium ceric nitrate and water is 500mL:2Kg-3Kg:12L-16L.
2. etching solution as claimed in claim 1, it is characterized in that, the proportioning of described ammonium ceric nitrate and water is less than or equal to 2Kg:12L.
3. etching solution as claimed in claim 1, it is characterized in that, the proportioning of described perchloric acid and water is less than or equal to 22.4mL: 0.6L.
4. etching solution as claimed in claim 1, it is characterized in that, the proportioning of described perchloric acid, ammonium ceric nitrate and water is 500mL:2Kg-3Kg:13L-14L.
5. etching solution as claimed in claim 1, it is characterized in that, the proportioning of described perchloric acid, ammonium ceric nitrate and water is 22.4mL: 0.1Kg: 0.6L.
6. etching solution as claimed in claim 1, it is characterized in that, described water is deionized water, and described etching solution is chromium plate etching solution.
7. a mask plate formation method, it comprises photoetching, development, etching and demoulding, it is characterized in that, described etching etches plate with the etching solution as described in any one of claim 1-6.
8. mask plate formation method as claimed in claim 7, it is characterized in that, described etching period is 50-70 second.
9. mask plate formation method as claimed in claim 7, it is characterized in that, described etching period is 60-64 second.
10. mask plate formation method as claimed in claim 7, it is characterized in that, every 12 liters of etching solutions are changed after etching more than 60 plates.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410650611.0A CN104375394A (en) | 2014-11-14 | 2014-11-14 | Etching liquor and mask plate forming method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410650611.0A CN104375394A (en) | 2014-11-14 | 2014-11-14 | Etching liquor and mask plate forming method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023024872A1 (en) * | 2021-08-23 | 2023-03-02 | 苏州贝克微电子股份有限公司 | Method and apparatus for establishing chip model in layout of chip, and storage medium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06250163A (en) * | 1993-02-24 | 1994-09-09 | A G Technol Kk | Light shielding film for display device |
| CN101548238A (en) * | 2007-11-06 | 2009-09-30 | 吉奥马科技有限公司 | Substrate for photomask, photomask, and method for manufacturing the same |
| CN101566799A (en) * | 2008-04-23 | 2009-10-28 | 中国科学院微电子研究所 | Method for preparing hollowed-out polyimide evaporation shadow mask |
-
2014
- 2014-11-14 CN CN201410650611.0A patent/CN104375394A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06250163A (en) * | 1993-02-24 | 1994-09-09 | A G Technol Kk | Light shielding film for display device |
| CN101548238A (en) * | 2007-11-06 | 2009-09-30 | 吉奥马科技有限公司 | Substrate for photomask, photomask, and method for manufacturing the same |
| CN101566799A (en) * | 2008-04-23 | 2009-10-28 | 中国科学院微电子研究所 | Method for preparing hollowed-out polyimide evaporation shadow mask |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023024872A1 (en) * | 2021-08-23 | 2023-03-02 | 苏州贝克微电子股份有限公司 | Method and apparatus for establishing chip model in layout of chip, and storage medium |
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Application publication date: 20150225 |