CN103021838B - Amorphous carbon processing method and etching method by adopting amorphous carbon as hard mask - Google Patents
Amorphous carbon processing method and etching method by adopting amorphous carbon as hard mask Download PDFInfo
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- CN103021838B CN103021838B CN201110296996.1A CN201110296996A CN103021838B CN 103021838 B CN103021838 B CN 103021838B CN 201110296996 A CN201110296996 A CN 201110296996A CN 103021838 B CN103021838 B CN 103021838B
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Abstract
The invention provides a method of processing the amorphous carbon which serves as a hard mask. The method comprises the steps of: providing a hard mask layer which is made of amorphous carbon; patterning the hard mask layer; and conducting boron ion injection on the patterned hard mask layer. The invention further provides an etching method by adopting amorphous carbon as the hard mask, and comprises the steps of: providing a semiconductor substrate, forming an aligned mark and substrate patterns on the semiconductor substrate, wherein a layer to be etched is arranged at the uppermost layer; depositing the hard mask layer on the layer to be etched, wherein the hard mask layer is made of the amorphous carbon; detecting the aligned mark through the amorphous carbon so as to align patterns on a mask edition to the substrate patterns; patterning the hard mask layer; conducting boron ion injection on the patterned hard mask layer to form a new patterned hard mask layer; and etching the layer to be etched by taking the new patterned hard mask layer as a mask. According to the technical scheme, the problems that boron doping amount is limited when the to-be-etched layer is etched and the process requirement is high when the hard mask layer is removed can be solved.
Description
Technical field
The present invention relates to field of semiconductor manufacture, particularly relate to a kind of processing method of the amorphous carbon as hard mask and adopt amorphous carbon as the lithographic method of hard mask.
Background technology
In semiconductor fabrication process now, because the photoresist used in the photoetching technique of advanced person is more and more thinner, and need to keep Etch selectivity, the use of hard mask is more and more extensively changed simultaneously.
The advantage that amorphous carbon has some other materials not possess as hard mask: the first, amorphous carbon has good light transmission, and the layer be more conducive in photoetching aims at (overlap); The second, amorphous carbon hardness is comparatively large, and other material has high etching selection ratio relatively; 3rd, amorphous carbon is a kind of material of very easy removal.
In order to improve the etching selection ratio of amorphous carbon further, also have some prior aries open at present, the such as patent No. is disclose a kind of method forming semiconductor device in the United States Patent (USP) of US 6939794, and the method comprises:
There is provided Semiconductor substrate, one deck is layer to be etched, and alignment mark;
On layer to be etched, form one deck amorphous carbon, described amorphous carbon is mixed with boron ion;
By the amorphous carbon detection alignment mark of boron-doping;
Pattern on mask plate, by the amorphous carbon detection alignment mark of boron-doping, is aimed at the pattern of substrate;
The amorphous carbon of patterning boron-doping;
With the amorphous carbon of patterning boron-doping for mask, etch semiconductor substrates.
In the formation method of above-mentioned semiconductor, improve the etching selection ratio of amorphous carbon by mixing boron, mixing of described boron ion is in amorphous carbon deposition process, introduces B
2h
6stream realizes, and sees that in this U.S. Patent Publication text, the 3rd hurdle 49 row is to 55 row.But, also there are some defects in said method, such as: along with boron ion mixes the raising of concentration, amorphous carbon light transmission is deteriorated, the pattern affected on mask plate is detected alignment mark by the amorphous carbon of boron-doping by this, aim at, the amorphous carbon of the patterning boron-doping after making and with the amorphous carbon of patterning boron-doping for mask, etch semiconductor substrates all becomes not accurate, therefore, the dosage mixing boron can not be too high, and in this U.S. Patent Publication text, the 3rd hurdle the 59th row also mentions this problem to the 3rd hurdle the 2nd row; Secondly, in the hard mask process of removal, when namely removing the amorphous carbon of boron-doping, need to introduce H
2or CF
4, require higher to the realization of technique.
In view of this, be necessary in fact a kind of processing method of the new amorphous carbon as hard mask is provided and adopts amorphous carbon as the lithographic method of hard mask, to overcome the defect of prior art.
Summary of the invention
The problem that the present invention solves proposes a kind of processing method of the new amorphous carbon as hard mask and employing amorphous carbon as the lithographic method of hard mask, using overcome existing employing amorphous carbon etch as hard mask time, limited and that when removing this hard mask layer, technological requirement the is higher problem of boron-doping dosage range.
For solving the problem, the invention provides a kind of processing method of the amorphous carbon as hard mask, comprising:
There is provided hard mask layer, the material of described hard mask layer is amorphous carbon;
Hard mask layer described in patterning;
Boron ion implantation is carried out to described patterned hard mask layer.
Alternatively, in described boron ion implantation step, injection direction is above the table of vertical described hard mask layer.
Alternatively, in described boron ion implantation step, the surface normal direction of injection direction and described hard mask layer forms an angle.
Alternatively, the scope of described angle is: 10-30 degree.
Alternatively, in described boron ion implantation step, implantation dosage scope is: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
Alternatively, in described boron ion implantation step, Implantation Energy scope is: 5 ~ 10KeV.
Alternatively, in described boron ion implantation step, comprise: injected once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation is carried out again, to realize 360 degree of boron ion implantations to described patterned hard mask layer.
Alternatively, after described boron ion implantation step, also annealing steps is carried out to described patterned hard mask layer.
The present invention also provides a kind of amorphous carbon that adopts as the lithographic method of hard mask, comprising:
Semiconductor substrate is provided, described Semiconductor substrate is formed with alignment mark and underlay pattern, and the superiors are layer to be etched;
Described layer to be etched on deposit hard mask layer, the material of described hard mask layer is amorphous carbon; Detect alignment mark by amorphous carbon, the pattern on mask plate and underlay pattern are aimed at;
Hard mask layer described in patterning;
Boron ion implantation is carried out to described patterned hard mask layer, forms new patterned hard mask layer;
With described new patterned hard mask layer for mask, etch described layer to be etched.
Alternatively, in described boron ion implantation step, injection direction is the upper surface of vertical described hard mask layer.
Alternatively, in described boron ion implantation step, the surface normal direction of injection direction and described hard mask layer forms an angle.
Alternatively, the scope of described angle is: 10-30 degree.
Alternatively, in described boron ion implantation step, implantation dosage scope is: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
Alternatively, in described boron ion implantation step, Implantation Energy scope is: 5 ~ 10KeV.
Alternatively, described layer to be etched on after deposit hard mask layer step, also carry out the step of deposit antireflection dielectric layer; Described in described patterning, hard mask layer step comprises:
Described antireflection dielectric layer forms photoresist, after exposure imaging, with the photoresist of patterning for antireflection dielectric layer described in mask etching and described hard mask layer;
Remove photoetching glue residue and antireflection dielectric layer.
Alternatively, in described boron ion implantation step, comprise: injected once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation is carried out again, to realize 360 degree of boron ion implantations to described patterned hard mask layer.
Alternatively, after etching described step layer to be etched, also carry out removing described new patterned hard mask layer step.
Alternatively, remove described new patterned hard mask layer and adopt dry etching to remove, dry etching main etching gas is O
2, auxiliary etching gas is CF
4, H
2in at least one.
Alternatively, after described boron ion implantation step, also annealing steps is carried out to described patterned hard mask layer.
Compared with prior art, the present invention has the following advantages: adopt and first detect alignment mark by amorphous carbon, the pattern of the pattern on mask plate and substrate is aimed at, then hard mask layer described in patterning; Avoiding amorphous carbon along with boron ion mixes the raising of concentration, and light transmission is deteriorated, and affects alignment precision; Afterwards boron ion implantation is carried out to described patterned hard mask layer, form new patterned hard mask layer, with described new patterned hard mask layer for mask, etch described layer to be etched, make whole etching process precisely and boron-doping dosage range is unrestricted.
In addition, boron ion implantation is at the patterned laggard row of hard mask layer, in other words, just at the surperficial boracic ion of amorphous carbon, due in etching process, what hard mask layer worked is mainly top layer, therefore, namely play the effect of hard mask, when removing this hard mask afterwards, CF only need be introduced in surface region
4or H
2, zone line still adopts the O of amorphous carbon
2remove, technique realization condition is relatively simple.
Accompanying drawing explanation
Fig. 1 is the process flow schematic diagram of the amorphous carbon as hard mask that the embodiment of the present invention provides;
Fig. 2-Fig. 3 is the intermediate structure schematic diagram formed according to the method in Fig. 1;
Fig. 4 is a kind of final structure schematic diagram formed according to the method in Fig. 1;
Fig. 5 is the another kind of final structure schematic diagram formed according to the method in Fig. 1;
Fig. 6 is the lithographic method schematic flow sheet of the employing amorphous carbon that also provides of invention the present embodiment as hard mask;
Fig. 7, Fig. 8 are the intermediate structure schematic diagrames formed according to the method in Fig. 6;
Fig. 9 is the structural representation of alignment procedures;
Figure 10 makes the intermediate structure schematic diagram formed after aiming at further;
Figure 11 is a kind of final structure schematic diagram formed according to the method in Fig. 6;
Figure 12 is the another kind of final structure schematic diagram formed according to the method in Fig. 6.
Embodiment
The present invention first adopts and is aimed at by the pattern of the pattern on mask plate by amorphous carbon detection alignment mark and substrate, then hard mask layer described in patterning; Avoiding amorphous carbon along with boron ion mixes the raising of concentration, and light transmission is deteriorated, and affects alignment precision; Afterwards boron ion implantation is carried out to described patterned hard mask layer, form new patterned hard mask layer, with described new patterned hard mask layer for mask, etch described layer to be etched, make whole etching process precisely and boron-doping dosage range is unrestricted.
In addition, boron ion implantation is at the patterned laggard row of hard mask layer, in other words, just at the surperficial boracic ion of amorphous carbon, due in etching process, what hard mask layer worked is mainly top layer, therefore, namely play the effect of hard mask, when removing this hard mask afterwards, CF only need be introduced in surface region
4or H
2, zone line still adopts the O of amorphous carbon
2remove, technique realization condition is relatively simple.
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Owing to focusing on, principle of the present invention is described, therefore, charts not in scale.
The processing method of the amorphous carbon as hard mask that the present embodiment provides, shown in Figure 1.
Composition graphs 1 and Fig. 2, first, perform step S11, provide hard mask layer 11, the material of described hard mask layer 11 is amorphous carbon; Structural section schematic diagram as shown in Figure 2.
Then, step S12 is performed, hard mask layer 11 described in patterning.
Described patterning step can comprise: at surperficial spin coating one deck photoresist of hard mask layer 11, described photoresist is very thin, and after selectivity exposure imaging, form the hard mask layer 11 of patterning, resulting structures schematic cross-section as shown in Figure 3.Further, for reaching the interference eliminating reverberation in exposure process, this step can also comprise: surface deposition antireflection dielectric layer (DARC) (not shown) of hard mask 11, then on described antireflection dielectric layer, photoresist is formed, after exposure imaging, with the photoresist of patterning for antireflection dielectric layer described in mask etching and described hard mask layer 11; Afterwards, photoetching glue residue and antireflection dielectric layer is removed.
Perform step S13, boron ion implantation is carried out to described patterned hard mask layer 11.
In specific implementation process, as improvements over the prior art, the injection direction of boron ion is the surface of vertical described hard mask layer, and this method for implanting can form the amorphous carbon mixing boron in upper surface 111 region of the hard mask layer 11 of patterning, resulting structures schematic cross-section as shown in Figure 4.
In this step, injection direction can also form an angle with upper surface 111 normal direction of described hard mask layer, this method for implanting can form in upper surface 111 region of the hard mask layer 11 of patterning and component side surface 112 region the amorphous carbon mixing boron, and resulting structures schematic cross-section as shown in Figure 5.Further, injection completes once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation is carried out again, to realize 360 degree of boron ion implantations to described patterned hard mask layer, this method for implanting can form in upper surface 111 region of the hard mask layer 11 of patterning and whole side surface 112 region the amorphous carbon mixing boron.
In specific implementation process, the present inventor finds that the scope of described angle is: 10-30 degree, injects effect better.
Inject vertical and become angle injection process, implantation dosage is relevant to required boron ion concentration, and Implantation Energy is relevant to required boron ion depth, and boron ion concentration is relevant to etching selection ratio, therefore, implantation dosage scope can be comparatively large, such as, be: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
As previously described, what hard mask layer played a major role in etching process is surface, and therefore, Implantation Energy does not need too high, and scope is such as: 5 ~ 10KeV.
In specific implementation process, for making boron ion distribution even, can also step S14 be performed, described patterned hard mask layer 11 is annealed.Described annealing temperature is such as 400 degree, and environment is such as N
2in, the duration is 10-15 minute such as.
The present embodiment additionally provides the lithographic method adopting amorphous carbon as hard mask, as shown in Figure 6.
Composition graphs 6 and Fig. 7, first perform step S21, provide Semiconductor substrate 21, described Semiconductor substrate 21 is formed with alignment mark 213 and underlay pattern 214, and the superiors be layer to be etched 215; Structural section schematic diagram as shown in Figure 7; In the present embodiment, described alignment mark 213 is generally some spiders, and underlay pattern 214 is generally the part-structure of device or the device that Semiconductor substrate is formed.
It should be noted that, in order to hint effect is considered, the alignment mark 213 in Fig. 7 and underlay pattern 214 have carried out transparent effect display.
Then, perform step S22, deposit hard mask layer 22 on described layer to be etched 215, the material of described hard mask layer 22 is amorphous carbon; Structural representation as shown in Figure 8.
Then, perform step S23, by amorphous carbon detection alignment mark 213, the pattern 30 on mask plate and underlay pattern 214 are aimed at.Alignment procedures schematic diagram as shown in Figure 9.
In this process, alignment mark 213 role is that the pattern 30 on auxiliary mask plate is aimed at the underlay pattern 214 be formed on substrate.
Then, step S24 is performed, hard mask layer 22 described in patterning.
Described patterning step can comprise: at surperficial spin coating one deck photoresist of hard mask layer 22, described photoresist is very thin, after selectivity exposure imaging, form the photoresist of patterning, then with the hard mask layer 22 of patterned photo glue for mask etching formation patterning; In order to illustrate conveniently, Figure 10 show hard mask layer 22 patterned after, and along the sectional structure schematic diagram of A-A straight line in Fig. 9.Further, eliminate in exposure process for reaching, the interference of reverberation, this step can also comprise: surface deposition antireflection dielectric layer (DARC) (not shown) of hard mask layer 22, then on described antireflection dielectric layer, photoresist is formed, after exposure imaging, with the photoresist of patterning for antireflection dielectric layer described in mask etching and described hard mask layer 22; Afterwards, photoetching glue residue and antireflection dielectric layer is removed.
Subsequently, perform step S25, boron ion implantation is carried out to described patterned hard mask layer, forms new patterned hard mask layer 22.
In specific implementation process, as improvements over the prior art, the injection direction of boron ion is the surface of vertical described hard mask layer, and this method for implanting can form the amorphous carbon mixing boron in upper surface 221 region of the hard mask layer 22 of patterning, resulting structures schematic cross-section as shown in figure 11.
In this step, injection direction also can form an angle with upper surface 221 normal direction of described hard mask layer, this method for implanting can form in upper surface 221 region of the hard mask layer 22 of patterning and component side surface 222 region the amorphous carbon mixing boron, and resulting structures schematic cross-section as shown in figure 12.Further, injection completes once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation is carried out again, to realize 360 degree of boron ion implantations to described patterned hard mask layer, this method for implanting can form in upper surface 221 region of the hard mask layer 22 of patterning and whole side surface 222 region the amorphous carbon mixing boron.
In specific implementation process, the present inventor finds that the scope of described angle is: 10-30 degree, injects effect better.
Inject vertical and become angle injection process, implantation dosage is relevant to required boron ion concentration, and Implantation Energy is relevant to required boron ion depth, and boron ion concentration is relevant to etching selection ratio, therefore, implantation dosage scope can be comparatively large, such as, be: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
As previously described, what hard mask played a major role in etching process is surface, and therefore, Implantation Energy does not need too high, and scope is such as: 5 ~ 10KeV.
In specific implementation process, for making boron ion distribution even, can also step S26 be performed, described patterned hard mask layer 22 is annealed.Described annealing temperature is such as 400 degree, and environment is such as N
2in, the duration is 10-15 minute such as.
And then, perform step S27, with described new patterned hard mask layer 22 for mask, etch described layer to be etched 214.Described etching can be dry etching.
Alternatively, perform step S28, remove described new patterned hard mask layer 22 step.
In specific implementation process, remove described new patterned hard mask layer 22 and adopt dry etching to remove, dry etching main etching gas is O
2, auxiliary etching gas is CF
4, H
2in at least one.
Be understandable that in the present embodiment, only have surface region to contain boron ion, therefore, when only having surface region to remove, only CF need be introduced
4or H
2, zone line still adopts the O of amorphous carbon
2remove, relative hard mask layer is boracic ion all, remove technique and implement relatively simple, and cost is low.
Although the present invention discloses as above with preferred embodiment, the present invention is not defined in this.Any those skilled in the art, without departing from the spirit and scope of the present invention, all can make various changes or modifications, and therefore protection scope of the present invention should be as the criterion with claim limited range.
Claims (19)
1. as a processing method for the amorphous carbon of hard mask, it is characterized in that, comprising:
There is provided hard mask layer, the material of described hard mask layer is amorphous carbon;
Hard mask layer described in patterning;
Boron ion implantation is carried out only to make the surperficial boracic ion of described amorphous carbon hard mask layer to described patterned hard mask layer.
2. the processing method of amorphous carbon according to claim 1, is characterized in that, in described boron ion implantation step, injection direction is the upper surface of vertical described hard mask layer.
3. the processing method of amorphous carbon according to claim 1, is characterized in that, in described boron ion implantation step, the surface normal direction of injection direction and described hard mask layer forms an angle.
4. the processing method of amorphous carbon according to claim 3, is characterized in that, the scope of described angle is: 10-30 degree.
5. the processing method of amorphous carbon according to claim 1, is characterized in that, in described boron ion implantation step, implantation dosage scope is: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
6. the processing method of amorphous carbon according to claim 5, is characterized in that, in described boron ion implantation step, Implantation Energy scope is: 5 ~ 10KeV.
7. the processing method of amorphous carbon according to claim 3, it is characterized in that, in described boron ion implantation step, comprise: injected once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then carry out twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation again, to realize 360 degree of boron ion implantations to described patterned hard mask layer.
8. the processing method of amorphous carbon according to claim 1, is characterized in that, after described boron ion implantation step, also carries out annealing steps to described patterned hard mask layer.
9. adopt amorphous carbon as a lithographic method for hard mask, it is characterized in that, comprising:
Semiconductor substrate is provided, described Semiconductor substrate is formed with alignment mark and underlay pattern, and the superiors are layer to be etched;
Described layer to be etched on deposit hard mask layer, the material of described hard mask layer is amorphous carbon;
Detect alignment mark by amorphous carbon, the pattern on mask plate and underlay pattern are aimed at;
Hard mask layer described in patterning;
Boron ion implantation is carried out only to make the surperficial boracic ion of described amorphous carbon hard mask layer to described patterned hard mask layer, forms new patterned hard mask layer;
With described new patterned hard mask layer for mask, etch described layer to be etched.
10. lithographic method according to claim 9, is characterized in that, in described boron ion implantation step, injection direction is the upper surface of vertical described hard mask layer.
11. lithographic methods according to claim 9, is characterized in that, in described boron ion implantation step, the surface normal direction of injection direction and described hard mask layer forms an angle.
12. lithographic methods according to claim 11, is characterized in that, the scope of described angle is: 10-30 degree.
13. lithographic methods according to claim 9, is characterized in that, in described boron ion implantation step, implantation dosage scope is: 5 × 10
14~ 1 × 10
15individual atom/square centimeter.
14. lithographic methods according to claim 13, is characterized in that, in described boron ion implantation step, Implantation Energy scope is: 5 ~ 10KeV.
15. lithographic methods according to claim 9, is characterized in that, described layer to be etched on after deposit hard mask layer step, also carry out the step of deposit antireflection dielectric layer; Described in described patterning, hard mask layer step comprises:
Described antireflection dielectric layer forms photoresist, after exposure imaging, with the photoresist of patterning for antireflection dielectric layer described in mask etching and described hard mask layer;
Remove photoetching glue residue and antireflection dielectric layer.
16. lithographic methods according to claim 9, it is characterized in that, in described boron ion implantation step, comprise: injected once, rotate described patterned hard mask layer 90 degree, carry out a boron ion implantation again, then carry out twice 90 degree of rotation to described patterned hard mask layer and twice boron ion implantation again, to realize 360 degree of boron ion implantations to described patterned hard mask layer.
17. lithographic methods according to claim 9, is characterized in that, after etching described step layer to be etched, also carry out removing described new patterned hard mask layer step.
18. lithographic methods according to claim 17, is characterized in that, remove described new patterned hard mask layer and adopt dry etching to remove, dry etching main etching gas is O
2, auxiliary etching gas is CF
4, H
2in at least one.
19. lithographic methods according to claim 9, is characterized in that, after described boron ion implantation step, also carry out annealing steps to described patterned hard mask layer.
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| SG11201600440VA (en) * | 2013-11-06 | 2016-02-26 | Mattson Tech Inc | Novel mask removal process strategy for vertical nand device |
| US20150235864A1 (en) * | 2014-02-17 | 2015-08-20 | Infineon Technologies Ag | Method for processing a layer and a method for manufacturing an electronic device |
| CN107968094A (en) * | 2017-11-21 | 2018-04-27 | 长江存储科技有限责任公司 | A kind of ledge structure forming technology for 3D nand flash memories |
| US11049728B2 (en) * | 2018-10-31 | 2021-06-29 | Entegris, Inc. | Boron-doped amorphous carbon hard mask and related methods |
| KR20210148674A (en) * | 2020-06-01 | 2021-12-08 | 에스케이하이닉스 주식회사 | Semiconductor device using hard mask and method for fabricating the same |
| CN112133626B (en) * | 2020-10-12 | 2023-06-06 | 成都海威华芯科技有限公司 | Manufacturing method of metal hard mask and wafer |
| CN113192958B (en) * | 2021-04-28 | 2022-01-04 | 长江存储科技有限责任公司 | Memory device and method of manufacturing the same |
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| CN1992227A (en) * | 2005-12-28 | 2007-07-04 | 海力士半导体有限公司 | Method of fabricating semiconductor device with dual gate structure |
| CN102136415A (en) * | 2010-01-27 | 2011-07-27 | 中芯国际集成电路制造(上海)有限公司 | Method for improving roughness of line edge of photoetching pattern in semiconductor process |
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| US6939794B2 (en) * | 2003-06-17 | 2005-09-06 | Micron Technology, Inc. | Boron-doped amorphous carbon film for use as a hard etch mask during the formation of a semiconductor device |
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| CN1992227A (en) * | 2005-12-28 | 2007-07-04 | 海力士半导体有限公司 | Method of fabricating semiconductor device with dual gate structure |
| CN102136415A (en) * | 2010-01-27 | 2011-07-27 | 中芯国际集成电路制造(上海)有限公司 | Method for improving roughness of line edge of photoetching pattern in semiconductor process |
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