CN1309029C - Treatment method of antireflection film SiON surface hydrogenplasma body - Google Patents
Treatment method of antireflection film SiON surface hydrogenplasma body Download PDFInfo
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- CN1309029C CN1309029C CNB021361223A CN02136122A CN1309029C CN 1309029 C CN1309029 C CN 1309029C CN B021361223 A CNB021361223 A CN B021361223A CN 02136122 A CN02136122 A CN 02136122A CN 1309029 C CN1309029 C CN 1309029C
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Abstract
SiON is a promising inorganic antireflection coating material, but has the defects of photoresist remaining on a basal film because amino groups (-NH2) and the photoresist react with each other, and the reaction greatly influences the accuracy of pattern transfer. How to reduce the influence of reflected light from a substrate forms a challenge since the photolithography in industrial production is shifted to deep ultraviolet short wavelength from 248 nm to 193 or 157 nm. The present invention adopts a hydrogen plasma method to make the surface of SiON rich in H<+> to prevent H<+> in photoresist shifting downwards, and thus, the present invention eliminates the problem of the photoresist remaining on the basal film.
Description
Technical field
The invention belongs to the semiconductor integrated circuit manufacturing process technology field, be specifically related to the surface treatment method of a kind of photoetching with inorganic anti-reflection film SiON
Background technology
The semiconductor chip manufacturing no longer is simply will to expose, develop after the photoresist spin coating and then etch the figure of oneself wishing on silicon chip, but the epoch that to use anti-reflective film and light-absorption layer have been entered, so just can achieve the goal, and show day important along with reducing of cell size.That is to say, before the spin coating photoresist, will deposit 2 or 3 layers---light-absorption layer+anti-reflective film its objective is prevention from the reverberation of substrate and incident light interference and the exposure that causes is inhomogeneous, as standing wave effect.
A kind of film is arranged bottom anti-reflection layer (BARC), be widely used in the photoetching process of the polysilicon gate of MOS transistor and connecting hole etc. at present.For these technology, critical dimension control is very important; But the less interconnection layer that is used for, TiN not only is used as anti-reflective film there, but also electromigration of may command aluminum steel and prevention aluminum steel are piled up.Yet because the control of critical dimension is more and more strict, this situation can change very soon.
Along with photoetching in the industrial production is shifted to the deep ultraviolet short wavelength---from 248nm to 193nm or 157nm, reducing becomes the focus that people pay close attention to from the catoptrical influence of substrate.Wavelength is shorter, and is stronger from the reflection of substrate, and relevant with interference problem---these problems have influenced the accuracy of litho pattern greatly to more for your demand side as a result; Simultaneously, photoetching technique such as phase shifted light are mechanical, off-axis throws light on and optical approximate has allowed people to print out the size littler than exposure wavelength, this makes that to reduce the size drift that reverberation brings very key, also is to impel semiconductor technology more to use another power of anti-reflective film.
How does anti-reflective film work? here do simple an introduction.When light by a kind of material or when running into certain interface, always transmission, absorption, reflection or refraction take place, this depends on the optical characteristics at medium and interface.Anti-reflective film is a kind of organic substance of spin coating usually as photoresist, or with the inorganic nitrogen oxide (as SiON) of PECVD deposition.
Organic and inorganic anti-reflection film is having a great difference aspect the prevention reverberation.The organic antireflecting film--produces such as BrewerScience, Clariant, Hitachi and the preparation of Tokyo Ohka company--that-its refractive index should be complementary with photoresist, if the two coupling is fine, the interface of photoresist and organic antireflecting film does not just have reflection so.These organic membrane have extinction characteristic, its can will enter the light of anti-reflective film before the lower surface reflection, sponge (or promptly be that lower surface has reflection, before entering photoresist, be absorbed).General deposit thicker of these organic membrane is usually at 60-120nm.
Inorganic anti-reflection film BARC utilizes disappear mutually principle preparation of the interference of light, even must be mutually opposite from the reverberation position of inorganic BARC upper and lower surface, and interfere and disappears mutually.This can realize by three parameters adjusting the inorganic BARC of SiON, that is: refractive index n, absorptivity k and thickness t.Company of Applied Materials uses a kind of SiON process for stabilizing based on helium to be easy to realize n, k, and the adjustment of t makes reverberation almost nil.Simultaneously, compare with the organic antireflecting film, helium can reduce the number of particles on SiON surface and increase its stability.
Semi-conductor industry is used spin coating organic antireflecting film at the beginning, and is widely used in 0.35 μ m technology first.The characteristics of organic BARC are that cost is few, and refractive index can repeat, and complanation degree good (in some application facet) is easy to deposit and removal, and the big and surface of thickness tolerance is easy to control.The characteristics of inorganic BARC are can deposit very thin film with the PECVD technology, and can control the uniformity (error is ± 1%) of thickness accurately; Be easy to adjust the deposition of the composition and the multilayer film of film.SiON has higher etching selection ratio to photoresist than organic membrane.
No matter be which kind of BARC of organic or inorganic, an important criterion is: BARC can not react or have the intermediate layer with the photoresist on it.For organic BARC, adopt the hinge coupling of BARC and photoresist usually or a kind ofly be insoluble to organic polymer, thereby suppress the formation in intermediate layer.For inorganic BARC, between inorganic BARC and photoresist, also has disadvantageous reaction.Archenemy is to be deposited in the lip-deep (NH of SiON
2) amido, and photoresist deep ultraviolet (DUV) photoresist particularly reacts with it; And this reaction can cause the appearance of photoresist counterdie (footing), and passes by relatively or old photoresist, and the new photoresist of DUV is retained more responsive to counterdie.
It is deposit skim oxide on BARC (as SiON) that a kind of method that solves the photoresist counterdie is arranged.From reporting of Applied Materials: in fact the oxide of this in-situ depositing can alleviate the counterdie effect, and it provides a kind of inert barrier between BARC and photoresist, and to the not influence of optical characteristics of BARC.
The another kind of method that solves the photoresist counterdie is: after the SiON deposit is finished, handle its surface with oxygen, thereby the amine (NH that causes counterdie
2) base remove from the surface.This is put forward by U.S. Novellus company.This technology has increased the N of original position
2O gas treatment (before silicon chip is taken out from deposition chamber).This deposit rear surface processing procedure may not only be removed the amine (NH on SiON surface
2) base, other benefit in addition.Such as, some new photoresists not with amine (NH
2) radical reaction, but connect group's reaction with other key of SiON surface.
In sum, in order to reduce the critical dimension drift that reverberation brings in photoetching, using anti-reflective film is the basic skills that is adopted in the DUV photoetching.People are studying and are using inorganic anti-reflection film at present, and SiON it is believed that up-and-coming a kind of material; Yet its shortcoming is: the retention problem of photoresist counterdie, this is in very big accuracy of deciding to have influenced on the degree figure transfer.Main cause is because the amido (NH on SiON surface
2) with due to the photoresist reaction; In other words, wherein H behind the resist exposure
+Shift to the SiON surface, caused the photoresist counterdie to retain problem.In order to overcome this shortcoming, people deposit the very thin oxide of one deck usually again or directly use its surface of oxygen treatments applied on SiON.How effectively to remove and to stop the amido (NH on SiON surface
2) react with photoresist, become the focus of people's research.
Summary of the invention
The objective of the invention is to propose a kind of deep ultraviolet light-sensitive lacquer counterdie that can effectively reduce and retain, improve the surface treatment method of anti-reflective film SiON film of the accuracy of figure transfer.
Utilize the interference of light principle to disappear mutually, thereby reduce or remove because the lithographic dimensioned drift that causes of reverberation (vides infra) as shown in Figure 1 from the reverberation of SiON film upper and lower surface.Photoresist generally is made of four parts: the agent of light enzyme, resin, solvent and additive.PAG (agent of light enzyme) produces H after illumination
+, in follow-up bake process, replace the protecting group R in the resin, thereby realize from insoluble to the transformation that is dissolved in developer solution, as shown in Figure 3.After photoresist, was exposed at spin coating, exposed portion produced a spot of acid or H
+Ion, as shown in Figure 2; And these H just
+Ion makes exposure as catalyst in bake process the developer solution that is partially soluble in, developing the back figure should be as far as possible near technological requirement.In general, film surface adsorption that is etched or inner the retention have attraction H
+The group of ion is as-OH, makes the H that the exposure back produces
+(the H certainly, of diffusion downwards
+Ion is simultaneously also to the both sides diffusion), greatly reduce H at the interface
+Concentration, cause photoresist counterdie (footing) to be retained, as shown in Figure 4.Retain in order effectively to eliminate counterdie, the present invention has taked the surface treatment method of following SiON film: go up deposit SiON reflectance coating with conventional plasma (PECVD) method at the substrate (as polycrystalline grid and metal) of desiring etching, carry out the surface physics bombardment with the Ar plasma earlier in position immediately then, purpose is to remove the more weak amido (NH of SiON film surface bond
2); Use H again
2With Ar or H
2Carry out surface treatment with the He hybrid plasma, make SiON film unsaturated amido in surface or NH
2+ be able to saturatedly, stop H in the photoresist
+Shift to the SiON surface, retain problem thereby eliminated the photoresist counterdie.As shown in Figure 5.
In the said method, the SiON film thickness of deposit is generally 20-30nm, specifically can decide according to different photoresists.The composition of this film is generally: Si:40-50%, and O:55-45%, N:5-6%, total amount is 100%.
In the said method, carry out the surface bombardment with the Ar plasma earlier, the time is 10-15 second.Use H
2+ Ar or H
2During the surface treatment of+He hybrid plasma, make surperficial rich hydrogen, hydrogenation time is 10-20 second.
The inventive method has significantly reduced the appearance of SiON photomask surface glue counterdie, thereby makes the drift of polysilicon gate oxygen critical dimension be greatly improved.Present technique technology is simple, and the anti-reflective film steady quality is easy to operate, is applicable to very much big production.
Description of drawings
Accompanying drawing 1 is the fundamental diagram of inorganic SiON anti-reflective film.Utilize the interference of light principle, the reverberation from the SiON upper and lower surface disappeared mutually, thereby reduce the influence of reverberation lithographic accuracy.
Accompanying drawing 2 is deep ultraviolet light-sensitive lacquer exposure and development schematic diagram.After photoresist, was exposed at spin coating, exposed portion produced a spot of acid or H
+Ion, and these H just
+Ion makes exposure as the catalyst (see figure 3) in bake process the developer solution that is partially soluble in.Developing the back figure should be as far as possible near technological requirement.
Accompanying drawing 3 is a kind of chemical molecular formula of deep ultraviolet light-sensitive lacquer and the situation of change after the illumination.Photoresist generally is made of four parts: the agent of light enzyme, resin, solvent and additive.PAG (agent of light enzyme) produces H after illumination
+, in follow-up bake process, replace the protecting group R in the resin, thereby realize from insoluble to the transformation that is dissolved in developer solution.
Accompanying drawing 4 is General Principle figure that the photoresist counterdie is retained.In general, film surface adsorption that is etched or inner the retention have attraction H
+The group of ion is as-OH (seeing as shown in the figure), makes the H that the exposure back produces
+(the H certainly, of diffusion downwards
+Ion is simultaneously also to the both sides diffusion), greatly reduce H at the interface
+Concentration, cause photoresist counterdie (footing) to be retained.
Accompanying drawing 5 is inorganic SiON surface amido (NH
2 +) with exposure back photoresist in H
+Reaction, photoresist fails to remove fully in developing process, thereby causes counterdie to be retained.
Number in the figure: 1 is that substrate, 2 is that inorganic anti-reflection film SiON, 3 is for preventing that counterdie oxide layer, 6 is that deep ultraviolet light-sensitive lacquer, 7 is a kind of anti-reflective film
Embodiment
Method that the invention is further illustrated by the following examples.
1.SiON deposit: at first grid oxygen and polysilicon or other above substrate with conventional plasma method (PECVD, such as the Cendura system of company of Applied Materials---DXZ PECVD deposition chamber) inorganic SiON anti-reflective film 20 of deposit or 30nm.
2.Ar bombardment: after the SiON deposit, use Ar plasma bombardment SiON surface 10-15 second in position immediately, purpose is to remove the weak amido (NH that connects in SiON surface
2);
3.Ar/He+H
2Plasma treatment: and then at same chamber with a small amount of Ar or He and H
2Hybrid plasma carries out surface treatment 10-20 second, makes the unsaturated amido (NH in SiON surface
2 +) be able to saturatedly, and make surperficial rich hydrogen, thereby prevent the appearance of photoresist counterdie (footing), silicon chip is taken out from the CVD deposition chamber, spin coating deep ultraviolet light-sensitive lacquer (time is no more than 24 hours between resist coating and the surface treatment, shorter better) then, as shown in Figure 5.
Claims (4)
1, the surface treatment method of SiON film in a kind of integrated circuit fabrication process, it is characterized in that: with plasma deposition method deposit SiON anti-reflective film on the substrate of desiring etching, carry out the surface physics bombardment with the Ar plasma earlier in position then, to remove the more weak amido of SiON film surface bond; And then use H
2+ Ar or H
2+ He hybrid plasma carries out surface treatment, makes the unsaturated amido in SiON film surface be able to saturated.
2, the surface treatment method of SiON film according to claim 1, the thickness that it is characterized in that film is at 20-30nm.
3, the surface treatment method of SiON film according to claim 1 is characterized in that carrying out the surface bombardment with the Ar plasma, and the time is 10-15 second.
4, the surface treatment method of SiON film according to claim 1 is characterized in that using H
2+ Ar or H
2When+He hybrid plasma carries out the surface hydriding processing, make surperficial rich hydrogen, hydrogenation time is 10-20 second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021361223A CN1309029C (en) | 2002-07-19 | 2002-07-19 | Treatment method of antireflection film SiON surface hydrogenplasma body |
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|---|---|---|---|
| CNB021361223A CN1309029C (en) | 2002-07-19 | 2002-07-19 | Treatment method of antireflection film SiON surface hydrogenplasma body |
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| CN1309029C true CN1309029C (en) | 2007-04-04 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956180B (en) * | 2010-07-14 | 2012-05-23 | 中国科学院电工研究所 | Antireflective film SiNx:H surface in-situ NH3 plasma treatment method |
| CN106435503B (en) * | 2016-11-02 | 2019-02-05 | 清华大学 | A kind of silicon oxide film and its deposition method of big positive temperature coefficient |
| EP3576163B1 (en) * | 2018-05-30 | 2021-01-27 | IMEC vzw | Method for in situ surface repassivation in back-contacted solar cells |
| CN109065447B (en) * | 2018-08-03 | 2021-02-26 | 北京中兆龙芯软件科技有限公司 | Power device chip and manufacturing method thereof |
| CN109256330A (en) * | 2018-09-06 | 2019-01-22 | 德淮半导体有限公司 | A kind of photolithography method |
| JP2022037944A (en) * | 2018-12-28 | 2022-03-10 | 日産化学株式会社 | Method for improving etching resistance of resist underlayer film by pretreatment using hydrogen gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228760B1 (en) * | 1999-03-08 | 2001-05-08 | Taiwan Semiconductor Manufacturing Company | Use of PE-SiON or PE-OXIDE for contact or via photo and for defect reduction with oxide and W chemical-mechanical polish |
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2002
- 2002-07-19 CN CNB021361223A patent/CN1309029C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6228760B1 (en) * | 1999-03-08 | 2001-05-08 | Taiwan Semiconductor Manufacturing Company | Use of PE-SiON or PE-OXIDE for contact or via photo and for defect reduction with oxide and W chemical-mechanical polish |
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Owner name: SHANGHAI HUAHONG (GROUP) CO., LTD.; APPLICANT Free format text: FORMER OWNER: SHANGHAI HUAHONG (GROUP) CO., LTD. Effective date: 20060908 |
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Effective date of registration: 20060908 Address after: 201203 No. 177 blue wave road, Zhangjiang hi tech park, Shanghai, Pudong New Area Applicant after: Shanghai Huahong (Group) Co., Ltd. Co-applicant after: Shanghai integrated circuit research and Development Center Co., Ltd. Address before: 18, Huaihai Road, Shanghai, No. 200020, building 918 Applicant before: Shanghai Huahong (Group) Co., Ltd. |
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