CN102543846B - Surface treatment method for strengthening aluminum process metal layer and light resistance adhesive force - Google Patents
Surface treatment method for strengthening aluminum process metal layer and light resistance adhesive force Download PDFInfo
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- CN102543846B CN102543846B CN201110232265.0A CN201110232265A CN102543846B CN 102543846 B CN102543846 B CN 102543846B CN 201110232265 A CN201110232265 A CN 201110232265A CN 102543846 B CN102543846 B CN 102543846B
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Abstract
The invention discloses a surface treatment method for strengthening an aluminum process metal layer and light resistance adhesive force, which is used in a method of coating photoresist on the metal layer. The metal layer and a metal barrier layer covering on the metal layer are manufactured on a substrate. The method mainly comprises the steps of gas containing oxygen is led in a reaction cavity chamber and conducted equal electrolytic dissociation, a metal stopping layer covering on the metal layer is conducted high temperature plasma oxidation process, a metallic oxide film on the surface of the metal stopping layer covering on the metal layer is generated, silicon substrate organic matter compound gas is led in the reaction cavity chamber, an adsorbed layer is generated by conducting chemisorption on silicon substrate organic matter compound on the surface of the metallic oxide film, redundant silicon substrate organic matter compound gas in the reaction cavity chamber is pumped out, only the adsorbed layer is retained, a first bonding intermediate layer is generated by the adsorbed layer under plasma activation reaction.
Description
Technical field
The present invention relates to a kind of field of semiconductor manufacture, relate in particular to a kind of surface treatment method that strengthens aluminum manufacturing procedure metal level and light resistance adhesive force.
Background technology
Along with improving constantly that semiconducting behavior requires, the size of integrated circuit (IC) chip is also more and more less, and photoetching process becomes operation most crucial in chip manufacturing.Common 45 complete nanometer technology chips, approximately need to 40 to 60 photo-mask processs depending on the difference of performance requirement.Along with dwindling of device size, the figure of photoetching also constantly dwindles, and the size after the more and more less and photoetching of the thickness of photoresistance completes is also more and more less.Along with chip production technique is from micron order state-of-the-art 15 nanometer technologies up till now, the wavelength that photoetching is used is also along with the progress of chip technology is constantly dwindled, from the I anchor line (string) of mercury, G anchor line (string) is to the 193nm ultraviolet ray of ultraviolet region, extreme ultraviolet line EUV and even electron beam.Photoetching becomes a precision processing technology.
The manufacture of chip has proposed very harsh process conditions to photoetching process, comprises edge roughness, size evenness, photoresistance Cross Section Morphology, defect etc.If photoresistance and substrate caking power are inadequate, can cause photoresist perk, the series of problems such as generation defect, etching undercutting come off.And photoresistance to come off be the most serious defect, can cause figure to lose efficacy, even cause sources of particles to jeopardize the region of periphery.Metal is due to its surperficial hydrophilic characteristics, than common oxide or silica-base film is more difficult combines closely with photoresist.Although adopt copper as interconnecting metal material in high-end technique, on current market, also have a large amount of 0.18 micron, 0.13 micron, so that the aluminium interconnection process that also adopts of 110 nanometer technologies.Because it is simple that aluminum manufacturing procedure has technique, cheap, functional, cost performance is higher, therefore the integrated circuit of aluminum manufacturing procedure at present and in following longer a period of time also by there being a larger market, particularly in application markets such as low and middle-end logic technology and dynamic random access memorys.Therefore how to avoid simply and effectively the photoresistance of aluminum metal layer in aluminum manufacturing procedure to come off, become a very valuable research topic.
Avoid coming off of photoresistance, most critical be the adhesive force that improves photoresistance and substrate.Comparatively the method for conventional several raising adhesive force has several as follows at present:
The enhancing photoresistance that integrated circuit manufacturing industry circle is at present general and the way of substrate caking power are to adopt the organic surperficial adhesion promotor of spin coating, and conventional is hmds (English: Hexamethyldisilazane is called for short HMDS) at present.The party's ratio juris is: photoresistance is a kind of organic compound, shows as hydrophobicity.And normally pass through etching in ic manufacturing process, and pickling, the crystal column surface after washing and dry grade is normally hydrophilic, is therefore difficult to comparatively firmly be combined with the direct formation of photoresistance.And HMDS is as a kind of surfactant, by the thin layer at surface-coated layer of surface activating agent, thickness is only one or two molecular layer, makes wafer substrate surface show as hydrophobicity, thereby can firmly combine with photoresist.And lower floor's substrate also can combine with surfactant layer very closely.Thereby reach the binding ability of improving photoresistance and substrate, the problem of avoiding photoresistance to come off.
Chinese patent (publication number CN1166798A is for microelectronic without amine photoresist adhesion promoters) has been recorded another kind of organic bonding promoter, and its principle and above-mentioned principle are similar.But the weak point of this surperficial adhesion promotion agent method is that the adhesive force improving is limited, and wish obtains higher binding ability and just must strengthen the consumption of adhesive, and the price of adhesive is all higher, has greatly increased cost.And adhesive is too thick can affect again the development of photoetching and the control of photoetching pattern and size.In addition, HMDS can produce amine, to the toxic effect of PR, can produce extra defect.
Referred in United States Patent (USP) (patent No. 6251804B1 Method for enhancing adhesion of photo-resist to silicon nitride surfaces).The method that this patent is invented is for strengthening the silicon nitride on polycrystalline silicon gate pole surface and the adhesive force of photoresist.This invention is mainly to introduce an oxidizing process, the deionized water that oxidant is dissolved ozone, and the mixed liquor of oxygen gas plasma or dioxysulfate water, improves the adhesion of silicon nitride layer and HMDS by changing nitrogen silicon dangling bonds.But the method is the strengthening for the nitride silicon based end of polysilicon gate, and does not make a search and set forth at the bottom of metal aluminum based for the aluminium interconnection process the present invention relates to.The chemism of metal, interface performance is all different from silicon nitride.
Another kind method is in United States Patent (USP) (patent No. 4332881A:Resist adhesion in integrated circuit processing), and this invention is divided into twice coating by photoresistance.First be coated with the photoresistance of layer, then high-temperature baking, makes photoresistance and substrate good combination, then carries out thicker light blockage coating, and thicker photoresistance can combine preferably with thinner photoresistance, thereby reaches the object that improves adhesion.But this method is subject to the impact of photoresistance performance, that can improve is limited.And, because needs are repeatedly coated with, the exposure ability of whole photoresistance is brought to adverse effect, as dimensional homogeneity be difficult to control, follow-up remove photoresist bring defect.In addition, the method also needs to be repeatedly coated with photoresist, has reduced production efficiency, has increased cost.
In the photoetching process of metallic aluminium, in order to eliminate metal reflective, form standing wave effect and improve deelectric transferred performance, toward contact meeting at aluminium superficial growth one deck titanium nitride barrier layer (TiN), so the three level stack structure on the barrier layer, lower floor's barrier layer/aluminium/upper strata shown in Fig. 1-1 normally.But titanium nitride layer is metallicity water-wetted surface equally, also face photoresistance adhesion weak and produce the problem that photoresistance coat of paint comes off.And the too thick resistance that also can increase interconnection line of the thickness of titanium nitride layer, reduce device performance.
This external Chinese patent (lithographic method of publication number 101882596A metal level), mentions a kind of method that improves metal level and photoresist adhesion in this invention.This invention is on chip outermost layer aluminum metal redistributing layer, before photoetching, with chemical corrosion liquid immersion corrosion metal level, thereby obtains a comparatively coarse surface, reaches the object of the adhesion that improves metallic aluminium and photoresistance.But the chemical corrosion of the method is very large to the corrosiveness of metallic aluminium, the loss of aluminium is very large.Because aluminum metal redistributing layer is the metal level of chip most surface, technique is thereafter to encapsulate.Therefore this aluminum metal layer thickness is very large, conventionally in 1000 ~ 4000 nanometers, is that several times to tens times of common metal interconnection layer is thick, so the easily etching material unaccounted-for (MUF) of chemical liquids.But for the memory chip of 65 nanometers or the logic chip of 0.15 micron, its metal interconnecting layer only has 600 ~ 900 nanometers, therefore chemical corrosion liquid is very large to the injury of common metal interconnection line, is difficult to control, so this kind of method is not suitable in common aluminum metal interconnection.In fact, in the claim of this invention, also explicitly pointing out its aluminum interconnection layer used is redistribution metal layer.
Above several method has its pluses and minuses, and is not the combination that is used in particular for improving conventional aluminium metal surface and photoresistance.And due to metal and the more difficult formation of organic bonding, so the adhesion of metallic substrates and photoresistance is more weaker than silicon or silicide substrate.
And along with the progress of technology, increasing metal and metallic compound can become the surface directly contacting with photoresistance.As the metal of electric capacity and half storey, metal line, metal hard mask version etc.The combination of metal surface and photoresist is more weak, and the photoresist of metal surface also more easily comes off.Therefore, how to find a kind of method can realize fast, cheap, method improves metal surface and photoresist adhesion becomes the important technology difficult problem that semiconductor industry is urgently to be resolved hurrily reliably.
Summary of the invention
Problem for above-mentioned existence, the object of this invention is to provide a kind of by metal aluminum based basal surface being carried out to preliminary treatment before photoresist coating, thereby change the chemical state on metallic aluminium surface, the adhesion of substrate and photoresist and adhesion-promoting layer is strengthened, thereby the phenomenon that reduces and even avoid photoresist to come off, improves photoetching process reliability of technology.
The object of the invention is to be achieved through the following technical solutions:
Strengthen a surface treatment method for metal level and light resistance adhesive force, be used on metal level and apply in photoresist method, wherein, in substrate, make metal level and cover the metal barrier on metal level, mainly comprise the following steps:
In reaction chamber, pass into oxygen-containing gas and oxygen-containing gas is carried out to plasma, the described metal barrier that covers metal level top is carried out to high-temperature plasma oxidizing thermal treatment, described in generation one deck is positioned at, cover the thin layer of metal oxide on the metal barrier surface of metal level top;
In reaction chamber, pass into silica-based organic substance chemical compound gas, on described thin layer of metal oxide surface, described silica-based organic substance compound is carried out chemisorbed and produces one deck adsorption layer, afterwards described silica-based organic substance chemical compound gas unnecessary in reaction chamber is detached, only retain and be positioned at the lip-deep adsorption layer of described thin layer of metal oxide;
Described adsorption layer is generated under plasma-activated reaction to one deck the first bonding transition zone, described thin layer of metal oxide and described the first bonding transition zone are used for strengthening HMDS or photoresistance and metal level and are positioned at the adhesion of the metal barrier of metal level top.
Above-mentioned enhancing aluminum manufacturing procedure metal level and the surface treatment method of light resistance adhesive force, wherein, be also provided with layer of metal barrier layer between described metal level and described substrate.
Above-mentioned enhancing aluminum manufacturing procedure metal level and the surface treatment method of light resistance adhesive force, wherein, described in cover the metal barrier on metal level material be titanium nitride (TiN).
Above-mentioned enhancing aluminum manufacturing procedure metal level and the surface treatment method of light resistance adhesive force, wherein, the material of the metal barrier between described metal level and substrate is the mixed layer of titanium (Ti) and titanium nitride.
Above-mentioned enhancing aluminum manufacturing procedure metal level and the surface treatment method of light resistance adhesive force, wherein, described metal level is aluminium or aluminium copper.
Above-mentioned a kind of surface treatment method that strengthens aluminum manufacturing procedure metal level and light resistance adhesive force, wherein, carries out in high-temperature plasma oxidizing thermal treatment step described aluminum metal layer substrate, and the temperature range of described high temperature is: 100 ℃-700 ℃.
Above-mentioned a kind of surface treatment method that strengthens aluminum manufacturing procedure metal level and light resistance adhesive force, wherein, carries out in high-temperature plasma oxidizing thermal treatment step described aluminum metal layer substrate, and described oxidizing gas is oxygen, ozone, any in carbon dioxide.
Compared with the prior art, beneficial effect of the present invention is:
By this high-temperature oxydation step, first can remove surperficial pickup and improve the whole uniformity of substrate.The more important thing is, surperficial hydrophilic metal can be oxidized to metal oxide, form M-O key, and these newly-generated thin oxide layer are hydrophobicity interfaces, surface roughness also improves, the adhesion of preliminary raising and photoresistance or HMDS.
Thereafter utilize gas to infiltrate absorption, then plasma reaction generates one deck and adheres to transition interface, therefore can significantly improve at the bottom of metal aluminum based the adhesion with photoresistance, reduces defect and photoresist obscission, lifting process reliability.
The thickness of metal oxide layer is only several nanometers, and thinner several to dozens of atomic layer level thickness that is about of the thickness of surface depletion layer.This double-layer films is surface chemistry binding ability for a change only, rather than for generation of certain pattern or device architecture, therefore very thin film can achieve the goal, and the thin layer of lower thickness can possess very large production efficiency and speed of production, is conducive to energy-conserving and environment-protective.
Processing method of the present invention, can also be for the photoetching process of doing over again after the first photoetching failure of aluminum metal layer.In the secondary photoetching process of doing over again, the surface state of metal polar plate is more severe than first photoetching, and the metal polar plate surface of doing over again is poorer with the direct cohesive force of photoresist.In this situation, apply surface treatment mode of the present invention and can improve more significantly cohesive force, reduce the generation of degumming phenomenon.
Accompanying drawing explanation
Figure 1A-Fig. 1 D is an a kind of embodiment schematic flow sheet that strengthens the surface treatment method of aluminum manufacturing procedure metal level and light resistance adhesive force of the present invention.
Fig. 1 E is that another of a kind of surface treatment method that strengthens aluminum manufacturing procedure metal level and light resistance adhesive force of the present invention changes routine schematic diagram.
Embodiment
Below in conjunction with schematic diagram and concrete operations embodiment, the invention will be further described.
As Figure 1A-1D, show a kind of surface treatment method that strengthens aluminum manufacturing procedure metal level and light resistance adhesive force of the present invention.Reference is accompanying drawing once, has provided preferred embodiment of method of the aluminum metal photoetching to having comprised the inventive method:
As shown in Figure 1A, preferably, in substrate 11, make metal level 12 and cover the metal barrier 13 on metal level 12, between metal level 12 and substrate 11, be also provided with layer of metal barrier layer 14.
Wherein, cover metal barrier 13 and the metal barrier 14 between metal level 12 and substrate 11 on metal level 12, preferably, its composition is the mixture of titanium (Ti) or titanium and titanium nitride (TiN).
In addition, metal level can be aluminum, can also be aluminium copper, for example, and containing the albronze of 5% percentage by weight copper.
In this step, can in substrate 11, make two-layer: i.e. metal level 12 and cover the metal barrier 3 on metal level 12.
As shown in Figure 1B, in reaction chamber (Chamer) (not indicating in figure), pass into oxygen-containing gas and oxygen-containing gas is carried out to plasma, to covering the metal barrier 13 of metal level 12 tops, carry out high-temperature plasma oxidizing thermal treatment, generate the thin layer of metal oxide 15 that one deck is positioned at metal barrier 13 surfaces that cover metal level 12 tops;
In this step, high-temperature plasma oxidizing thermal treatment, under hot environment, utilization passes into institute's oxygen in reaction chamber, ozone, carbon dioxide or other oxygen-containing gass carry out plasma, and metal level 12 or metal barrier 13 are carried out to thermal oxidation, in the present embodiment, the optional scope of temperature is 100 ℃ ~ 700
oc, wherein, the plasma reaction of oxygen or ozone or other oxygen-containing gass carries out oxidation reaction, and the method reaction has active high, and reaction speed is fast, is conducive to the feature of the optimization of energy consumption and output.For example, can use common boiler tube oxygen atmosphere to process or ozone treatment.Practical application is according to reaction speed, the temperature of device tolerance, and the factors such as cleaning efficiency, select suitable oxidation processes mode and parameter.
As shown in Figure 1 C, in reaction chamber, pass into silica-based organic substance chemical compound gas, on thin layer of metal oxide 14 surfaces, silica-based organic substance compound is carried out chemisorbed and produces one deck adsorption layer 16, afterwards silica-based organic substance chemical compound gas unnecessary in reaction chamber is detached, only retain and be positioned at the lip-deep adsorption layer 16 of thin layer of metal oxide 15;
In one embodiment, silica-based organic substance chemical compound gas can be selected tetraethoxysilane, in addition, and the organic compound that can also select other to contain silicon or carbon.
As shown in Fig. 1 D, adsorption layer 16 is generated under plasma-activated reaction to one deck one bonding transition zone 17, thin layer of metal oxide 15 and bonds transition zone 17 for strengthening HMDS or photoresistance and metal level 12 and being positioned at the adhesion of the metal barrier 13 of metal level 12 tops.
In this step, HMDS is as a kind of surfactant, and by the thin layer at surface-coated layer of surface activating agent, thickness is only one or two molecular layer, makes wafer substrate surface show as hydrophobicity, thereby can firmly combine with photoresist.And lower floor's substrate also can combine with surfactant layer very closely.In the present embodiment, can combine with the first adhesion promotion layer 14, reach better the binding ability of improving photoresistance and substrate, the problem of avoiding photoresistance to come off.
As shown in Fig. 1 E, at one, change in example, can directly in substrate 21, make layer of metal layer 22, and directly on metal level 22, carry out successively the shown step of above-mentioned 1B-1C: metal level 22 is carried out to high-temperature plasma oxidizing thermal treatment and generate thin layer of metal oxide 25, carry out chemisorbed step generation adsorption layer 26, carry out adsorption layer 26 plasma activation reactions and generate bonding transition zones 27.
Above specific embodiments of the invention be have been described in detail, but the present invention is not restricted to specific embodiment described above, it is just as example.To those skilled in the art, any equivalent modifications that this is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (7)
1. strengthen a surface treatment method for metal level and light resistance adhesive force, be used on metal level and apply in photoresist method, wherein, in substrate, make metal level and cover the metal barrier on metal level, it is characterized in that, mainly comprise the following steps:
In reaction chamber, pass into oxygen-containing gas and oxygen-containing gas is carried out to plasma, the described metal barrier that covers metal level top is carried out to high-temperature plasma oxidizing thermal treatment, described in generation one deck is positioned at, cover the thin layer of metal oxide on the metal barrier surface of metal level top;
In reaction chamber, pass into silica-based organic substance chemical compound gas, on described thin layer of metal oxide surface, described silica-based organic substance chemical compound gas is carried out chemisorbed and produces one deck adsorption layer, afterwards described silica-based organic substance chemical compound gas unnecessary in reaction chamber is detached, only retain and be positioned at the lip-deep adsorption layer of described thin layer of metal oxide;
Described adsorption layer is generated under plasma-activated reaction to one deck the first bonding transition zone, described thin layer of metal oxide and described the first bonding transition zone are used for strengthening HMDS or photoresistance and metal level and are positioned at the adhesion of the metal barrier of metal level top.
2. the surface treatment method of enhancing metal level according to claim 1 and light resistance adhesive force, is characterized in that, between described metal level and described substrate, is also provided with layer of metal barrier layer.
3. the surface treatment method of enhancing metal level according to claim 1 and light resistance adhesive force, is characterized in that, described in cover the metal barrier on metal level material be titanium nitride (TiN).
4. the surface treatment method of enhancing metal level according to claim 3 and light resistance adhesive force, is characterized in that, the material of the metal barrier between described metal level and substrate is the mixed layer of titanium (Ti) and titanium nitride.
5. the surface treatment method of enhancing metal level according to claim 1 and light resistance adhesive force, is characterized in that, described metal level is aluminium or aluminium copper.
6. the surface treatment method of enhancing metal level according to claim 1 and light resistance adhesive force, is characterized in that, described metal barrier is carried out in high-temperature plasma oxidizing thermal treatment step, and the temperature range of described high temperature is: 100 ℃-700 ℃.
7. the surface treatment method of enhancing metal level according to claim 1 and light resistance adhesive force, it is characterized in that, described metal barrier is carried out in high-temperature plasma oxidizing thermal treatment step, and described oxidizing gas is oxygen, ozone, any in carbon dioxide.
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| CN104617111B (en) * | 2015-02-03 | 2017-08-25 | 京东方科技集团股份有限公司 | Substrate and its manufacture method, display device |
| 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 |
| CN111244114B (en) * | 2020-02-10 | 2023-10-17 | Tcl华星光电技术有限公司 | display panel |
| CN113725245B (en) * | 2021-09-06 | 2024-03-15 | 上海集成电路装备材料产业创新中心有限公司 | Pixel structure, microlens array, image sensor and manufacturing method of CIS chip |
| CN118888564B (en) * | 2024-09-29 | 2024-12-20 | 山西创芯光电科技有限公司 | Preparation method of indium column array with regular shape |
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| US6251804B1 (en) * | 2000-05-22 | 2001-06-26 | United Microelectronics Corp. | Method for enhancing adhesion of photo-resist to silicon nitride surfaces |
| CN1405843A (en) * | 2001-09-19 | 2003-03-26 | 旺宏电子股份有限公司 | Method for reducing photoresist roughness |
| CN1473352A (en) * | 2000-10-31 | 2004-02-04 | Ħ��������˾ | Amorphous carbon layer for improved photoresist adhesion |
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| US8357617B2 (en) * | 2008-08-22 | 2013-01-22 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method of patterning a metal gate of semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251804B1 (en) * | 2000-05-22 | 2001-06-26 | United Microelectronics Corp. | Method for enhancing adhesion of photo-resist to silicon nitride surfaces |
| CN1473352A (en) * | 2000-10-31 | 2004-02-04 | Ħ��������˾ | Amorphous carbon layer for improved photoresist adhesion |
| CN1405843A (en) * | 2001-09-19 | 2003-03-26 | 旺宏电子股份有限公司 | Method for reducing photoresist roughness |
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