CN102610516B - Method for improving adhesion force between photoresist and metal/metallic compound surface - Google Patents
Method for improving adhesion force between photoresist and metal/metallic compound surface Download PDFInfo
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- CN102610516B CN102610516B CN201110206446.6A CN201110206446A CN102610516B CN 102610516 B CN102610516 B CN 102610516B CN 201110206446 A CN201110206446 A CN 201110206446A CN 102610516 B CN102610516 B CN 102610516B
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Abstract
The invention relates to the field of manufacturing semiconductors, in particular relating to a method for improving an adhesion force between photoresist and a metal/metallic compound surface. The method comprises the following steps of: adding oxidation atmosphere in a traditional process flow, oxidizing metal on the upper surface of the metal/metallic compound, and growing an adhersion transition layer so as to modifying the adhesion force of the upper surface of the metal/metallic compound and the photoresist, reduce the risk of photoresist removal and generation of process defect, and improve the process stability and the yield of devices.
Description
Technical field
The present invention relates to field of semiconductor manufacture, particularly relate to a kind of method improving adhesion between photoresist and metal/metal compound surface.
Background technology
What require along with semiconducting behavior improves constantly, the size of integrated circuit (IC) chip is also more and more less, and the 45 nanometer technology chips that complete, the difference depending on performance requirement approximately needs 40 to 60 photo-mask processs, so photoetching process just becomes operation most crucial in chip manufacturing.Along with the figure of photoetching is also constantly reducing due to reducing of device size, the size after causing the thickness of photoresist and photoetching to complete is also more and more less, and namely photoetching becomes a precision processing technology.Such as, along with chip production process is from micron order nanometer technology up till now, the wavelength that photoetching uses is also along with the progress of chip technology is constantly reduced, from the I anchor line (string) of mercury, G anchor line (string) is to the 193nm ultraviolet of ultraviolet region, extreme ultraviolet line (extreme ultraviolet is called for short EUV) and even electron beam.
Current, the manufacture of chip proposes very harsh process conditions to photoetching process, comprises edge roughness, size evenness, photoresist (Photoresist is called for short PR) Cross Section Morphology, defect etc.Not, can cause the series of problems such as photoresist tilts, come off generation defect, etching undercutting, wherein, it is defect the most serious that photoresist comes off, and figure can be caused to lose efficacy, and even causes sources of particles to jeopardize the region of periphery for photoresist and substrate caking power.
Due to the hydrophilic characteristics of metal surface, and photoresist shows as hydrophobicity, thus causes metal than common oxide or silica-base film is more difficult combines closely with photoresist.Along with metal-insulator-metal (metal-insulator-metal is called for short MIM), capacitance structure obtains applying more and more widely in microwave or radio frequency chip, and the top crown of this kind of electric capacity is exactly metal or metallic compound.Therefore, how to avoid photoresist to come off simply and effectively, become a very valuable research topic.
Avoid coming off of photoresist, it is crucial that improve the adhesive force of photoresist and substrate.The method of several raising adhesive force comparatively conventional at present has several as follows:
The way of the enhancing photoresist that integrated circuit manufacturing industry circle is general at present and substrate caking power adopts the organic surface adhesive promoter of spin coating, and conventional is hmds (Hexamethyldisilazane is called for short HMDS) at present.Because photoresist is a kind of organic compound, show as hydrophobicity, and the crystal column surface after the technique such as etching, pickling, washing, drying in ic manufacturing process to be generally be hydrophilic metal/metal compound, be therefore difficult to directly be formed with photoresist be comparatively firmly combined.
As Figure 1-3, be conventional lithography process flowage structure schematic diagram.First on the upper surface of the electric pole plate 11 of mim capacitor structure 1, spin coating organic surface adhesive Urotropinum MDS molecular layer 12 covers top crown 11, and then spin coating photoresist 13 covers HMDS molecular layer 12, exposes, developing process to photoresist 13.HMDS molecular layer 12 is as a kind of surfactant, by the HMDS molecular layer 12 at electric pole plate 11 surface-coated layer of surface activating agent, its thickness is only one or two molecular layer, the upper strata of HMDS molecular layer 12 and the lower surface of photoresist 13 combine, the lower floor of HMDS molecular layer 12 and the upper surface of electric pole plate 11 also can combine very closely, thus improve photoresist 13 and the binding ability of electric pole plate 11, avoid the problem that photoresist 13 comes off; But the adhesive force of HMDS molecular layer is limited, and the gas in exposure, developing process, liquid, high temperature all can to the photoresist 13 retained
1generation effect, because adhesion is not enough to resist above-mentioned effect, the photoresist 13 retained
1will tilt, come off, thus figure is changed and process failure, HMDS can produce amine simultaneously, not only to the toxic effect of PR, also can produce extra defect.
Chinese patent (publication number 1166798, for microelectronic without amine photoresist adhesion promoters) discloses a kind of organic bonding promoter, its principle and above-mentioned principle similar.But the weak point of the surface adhesive promoter method recorded in this patent is that the adhesive force improved is limited, and the consumption of adhesive just must be strengthened for obtaining higher binding ability, and adhesive too thick can affect photoetching development and photoetching pattern, size control, and the price of adhesive is higher, cause its cost intensive.
United States Patent (USP) (patent No. US6251804B1, strengthen the method (Method for enhancing adhesion of photo-resist to silicon nitride surfaces) of the silicon nitride on polycrystalline silicon gate pole surface and the adhesive force of photoresist) disclose a kind of method of adhesive force of silicon nitride and photoresist for strengthening polycrystalline silicon gate pole surface, it mainly introduces an oxidizing process, oxidant is the deionized water of dissolved ozone, the mixed liquor of oxygen gas plasma or dioxysulfate water, the adhesion of silicon nitride layer and HMDS is improved by changing nitrogen silicon dangling bonds.But this invention is the strengthening at the nitride silicon based end for polysilicon gate, and sets forth metal/metal compound substrate.
United States Patent (USP) (patent No. US4332881A, the adhesion process (Resist adhesion in integrated circuit processing) in integrated circuit) discloses a kind of technique photoresist being divided into twice coating.First be coated with the photoresist of layer, then high-temperature baking, make photoresist and substrate good combination, then carry out thicker photoresist coating, can combine preferably compared with thick photoresist and thinner photoresist, thus reach the object improving adhesion.But this method by photoetching colloidality can impact, the adhesion that can improve is also limited, and is repeatedly coated with due to needs, brings adverse effect to the exposure capability of overall photoresist, as dimensional homogeneity be difficult to control, follow-up remove photoresist bring defect etc.; In addition, the method also needs repeatedly to be coated with photoresist, causes the rising of production efficiency reduction and process costs.
Due to metal and the more difficult formation of organic bonding, therefore, the adhesion of metal/metal compound substrate and photoresist is more weaker than silicon or silicide substrate.Though and above-mentioned several method has its advantage, the adhesion of metal/metal compound substrate surface and photoresist all openly effectively can not improved.
Along with the progress of technology, increasing metal/metal compound substrate can become the surface directly contacted with photoresist, as the metal polar plate layer of electric capacity, and metal line, metal hard mask plate etc.Therefore, how to find a kind of method can realize fast, cheap, that reliably method improves between metal/metal compound surface and photoresist adhesion becomes a semiconductor industry important technology difficult problem urgently to be resolved hurrily.
Summary of the invention
The invention discloses a kind of method improving adhesion between photoresist and metal/metal compound surface, the upper surface of the mim structure that semiconductor device comprises is provided with metal/metal compound layer, wherein, comprises the steps:
Step S1: utilize the plasma of oxygen-containing gas to carry out oxidation reaction to the upper surface of metal/metal compound layer under the high temperature conditions, makes the burning on the upper surface of metal/metal compound layer be metal oxide;
Step S2: utilize the plasma of silica-based organic gas to process metal oxide, forms the bonding transition zone of the upper surface of covering metal/metal compound layer;
Step S3: apply adhesion-promoting layer on bonding transition zone after, then spin coating photoresist or direct at the spin coating photoresist on transition zone that bonds.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, in step S1, the scope of high temperature is 100-700 DEG C.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, in step S1, oxygen-containing gas is oxygen, ozone, carbon dioxide etc.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, the silica-based organic gas in step S2 is the organic compound gas containing silicon, carbon, hydrogen etc., the preferably gas such as methane, dimethylsilane.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, the thickness of the transition zone that bonds in step S2 is several thickness to dozens of atomic layer.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, the material of described adhesion-promoting layer is hmds.
The method of adhesion between described raising photoresist and metal/metal compound surface, wherein, the material of described metal/metal compound layer is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride or tungsten etc.
In sum, owing to have employed technique scheme, the present invention proposes a kind of method improving adhesion between photoresist and metal/metal compound surface, by adding oxidizing atmosphere in traditional technological process, the metal of oxidized metal/metal compound layer upper surface, and grow one deck adhesive transition layer thereon, thus improve the adhesive force of metal/metal compound layer upper surface and photoresist, to reduce the generation of risk that photoresist comes off and defective workmanship, improve the yield of technology stability and device.
Accompanying drawing explanation
Fig. 1-3 is conventional lithography process flowage structure schematic diagrames in background technology of the present invention;
Fig. 4-7 is flowage structure schematic diagrames that the present invention improves the method for adhesion between photoresist and metal/metal compound surface.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described:
As shown in figs. 4-7, the invention provides a kind of method improving adhesion between photoresist and metal/metal compound surface, be sequentially set with the first pole plate 21, dielectric layer 22 on the substrate 2 from bottom to up.Wherein, first pole plate 21 can be reserved have the copper of certain figure or the metal interconnecting wires of aluminium, also can be utilize metallic aluminium deposited by physical vapour deposition (PVD), copper, tantalum, tantalum nitride, titanium, titanium nitride to equal the metal/metal compound layer that substrate 2 is formed; Dielectric layer 22 is for utilizing chemical vapour deposition (CVD) (Chemical Vapor Deposition, be called for short CVD), ald (Atomic layer deposition, be called for short ALD) or boiler tube growth technique, first pole plate 21 grows one deck containing silica, silicon nitride, silicon oxynitride, carborundum, the insulation dielectric layer of any one or a few the high-k in fire sand, hafnium oxide or aluminium oxide.
First, at the second pole plate 23 that dielectric layer 22 upper surface growth material is the metal/metal compounds such as aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride or tungsten, after forming the MIM capacitor mechanism of three level stack structure, to control within the scope of 100-700 DEG C under prerequisite in temperature, adopt oxygen-containing gas as gases such as oxygen, ozone, carbon dioxide, the upper surface of preferred employing oxygen to the second pole plate 23 carries out high-temperature oxydation Technology for Heating Processing, to be oxidized burning on the upper surface of the second pole plate 23 for metal oxide.In actual production process; owing to being ready to carry out photoetching at the bottom of capacitive-based; there is a stand-by period; particle or other defect may be produced; and also certain defect and inhomogeneities can be there is in the growth course of the second pole plate 23; effectively can eliminate by high-temperature oxydation Technology for Heating Processing the pickup or other defect that the second pole plate 23 may exist on the surface, return to the clean surface of atom level.The present embodiment preferably adopt oxygen gas plasma carry out high-temperature oxydation Technology for Heating Processing can intensified response active, thus reduce reaction temperature, to shorten the process time, and then reduce energy consumption, increase yield.According to reaction speed in actual preparation technology, the temperature of device tolerance, the factors such as cleaning efficiency, select suitable oxidation processes mode and parameter.
Then, after high-temperature oxydation Technology for Heating Processing completes, adopt siliceous, carbon, hydrogen organic compound gas, as the gas such as methane, dimethylsilane, under plasma-activated effect, the upper surface of above-mentioned organic compound gas and the second pole plate 23 generates the bonding transition zone 24 of layer of metal-silicon-oxygen, and the thickness of bonding transition zone 24 is several thickness to dozens of atomic layer.Now, the hydrophilic metal atomic layer of the upper surface of the second pole plate 23 is modified as the bonding transition zone 24 be more easily combined with photoresist or HMDS adhesion promotion layer 25, thus its adhesion is greatly strengthened.According to the amplitude that required adhesion promotes in actual preparation technology, select reactant and response parameter.
Finally, splash HMDS steam forms the HMDS adhesion promotion layer 25 covering bonding transition zone 24, and its thickness is the thickness of several molecular layer; Spin coating photoresist 26 covers HMDS adhesion promotion layer 25, after exposure, development, and the graphic structure of preparation definition, owing to changing the water-wet behavior of the upper surface of the second pole plate 23, remaining photoresist 26
1not easily produce the appearance of peeling and the defect that comes off.
Wherein, the order between high-temperature oxydation Technology for Heating Processing and the technique generating bonding transition zone can be inverted, and also can only adopt the arbitrary technique in two techniques to be prepared.
Owing to have employed the technique of high-temperature oxydation Technology for Heating Processing and generation bonding transition zone, adhesion between photoresist and metal/metal compound layer is strengthened greatly, therefore effectively control the peeling of photoresist and come off, thus improving reliability and the yield of technique.
Further, the present invention improves the method for adhesion between photoresist and metal/metal compound surface, also can be used on and does over again in photoetching process.First, by the wafer after the exposure imaging of failure, through the technology of removing photoresist of routine, after ashing and pickling, to remove the impurity such as photoresistance, HMDS of crystal column surface.Then, adopt the processing step similar with embodiment one, through high-temperature plasma oxidation processes, organic pickup that removal may remain and acid remain, and improve crystal column surface state, obtain clean surface; Thereafter, utilize the organic compound plasma of siliceous, carbon etc. to generate bonding transition zone, with the cohesive force of the metal/metal compound layer after improving photoresist and doing over again, thus reduce the peeling of photoresist and the appearance of the defect that comes off.
In sum, owing to have employed technique scheme, the present invention proposes a kind of method improving adhesion between photoresist and metal/metal compound surface, by high-temperature oxydation Technology for Heating Processing, effectively remove the pickup on metal/metal compound substrate surface and uneven state, and change the hydrophilicity of metal/metal compound substrate, thereafter gas is utilized to infiltrate absorption, then plasma reaction generates one deck and adheres to transition zone, to improve metallic substrates and photoresistance or the adhesion with HMDS, reduce defect and photoresist obscission, lifting process reliability and yield.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (5)
1. improve a method for adhesion between photoresist and metal/metal compound surface, the upper surface of the mim structure that semiconductor device comprises is provided with metal/metal compound layer, it is characterized in that, comprises the steps:
Step S1: utilize the plasma of oxygen-containing gas to carry out oxidation reaction to the upper surface of metal/metal compound layer under the temperature conditions of 100-700 DEG C, makes the burning on the upper surface of metal/metal compound layer be metal oxide;
Step S2: utilize the plasma of silica-based organic gas to process metal oxide, forms the bonding transition zone of the upper surface of covering metal/metal compound layer;
Step S3: apply adhesion-promoting layer on bonding transition zone after, then spin coating photoresist or direct at the spin coating photoresist on transition zone that bonds.
2. the method for adhesion between raising photoresist according to claim 1 and metal/metal compound surface, it is characterized in that, in step S1, oxygen-containing gas is oxygen, ozone, carbon dioxide.
3. the method for adhesion between raising photoresist according to claim 1 and metal/metal compound surface, it is characterized in that, the silica-based organic gas in step S2 is the organic compound gas containing silicon, carbon, hydrogen.
4. the method for adhesion between raising photoresist according to claim 1 and metal/metal compound surface, it is characterized in that, the material of described adhesion-promoting layer is hmds.
5. the method for adhesion between raising photoresist according to claim 1 and metal/metal compound surface, it is characterized in that, the material of described metal/metal compound layer is aluminium, copper, tantalum, tantalum nitride, titanium, titanium nitride or tungsten.
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| JP6495025B2 (en) | 2014-01-31 | 2019-04-03 | ラム リサーチ コーポレーションＬａｍ Ｒｅｓｅａｒｃｈ Ｃｏｒｐｏｒａｔｉｏｎ | Vacuum integrated hard mask processing and equipment |
| CN104835727B (en) * | 2014-02-11 | 2017-08-25 | 北大方正集团有限公司 | Semiconductor devices backplate preparation method |
| CN108666325B (en) * | 2018-05-24 | 2021-01-22 | 京东方科技集团股份有限公司 | Preparation method of TFT substrate, TFT substrate and display device |
| KR20210076999A (en) | 2018-11-14 | 2021-06-24 | 램 리써치 코포레이션 | Methods for making useful hard masks in next-generation lithography |
| US20220365434A1 (en) * | 2019-10-02 | 2022-11-17 | Lam Research Corporation | Substrate surface modification with high euv absorbers for high performance euv photoresists |
| CN110660839B (en) * | 2019-11-13 | 2022-04-29 | 京东方科技集团股份有限公司 | Display panel and preparation method thereof |
| CN110854075B (en) | 2019-11-13 | 2022-10-18 | 上海华力集成电路制造有限公司 | CMOS device manufacturing method |
| KR102539806B1 (en) | 2020-01-15 | 2023-06-05 | 램 리써치 코포레이션 | Underlayer for photoresist adhesion and dose reduction |
| CN115373056B (en) * | 2022-07-29 | 2024-04-05 | 深圳通感微电子有限公司 | Microlens and method for manufacturing same |
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| EP0792195A4 (en) * | 1994-11-22 | 1999-05-26 | Complex Fluid Systems Inc | Non-aminic photoresist adhesion promoters for microelectronic applications |
| JPH1041222A (en) * | 1996-07-23 | 1998-02-13 | Japan Energy Corp | Manufacture of semiconductor device |
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| CN1166798C (en) * | 2001-03-14 | 2004-09-15 | 中国科学院金属研究所 | Wear-resistant Co-base alloy material |
| CN101431015B (en) * | 2007-10-23 | 2010-12-01 | 应用材料股份有限公司 | Plasma surface treatment to prevent pattern collapse in immersion lithography |
| CN101719469A (en) * | 2009-11-10 | 2010-06-02 | 上海宏力半导体制造有限公司 | Method for manufacturing CVD silicon oxide capable of improving forming quality |
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