CN103631092A - Formation method for semiconductor structure - Google Patents
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- CN103631092A CN103631092A CN201210312959.XA CN201210312959A CN103631092A CN 103631092 A CN103631092 A CN 103631092A CN 201210312959 A CN201210312959 A CN 201210312959A CN 103631092 A CN103631092 A CN 103631092A
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Abstract
Provided is a formation method for a semiconductor structure. The method comprises a semiconductor substrate. A device layer is arranged on the surface of the semiconductor substrate. An anti-reflection film is formed on the surface of the device layer. The anti-reflection film contains fluorinated polymers. The anti-reflection film is subjected to thermal annealing, thus the anti-reflection film is formed into a first anti-reflection layer located on the surface of the device layer and a barrier layer located on the surface of the first anti-reflection layer. After the thermal annealing, a photoresist layer is formed on the surface of the barrier layer, and the photoresist layer defines positions which need etching. The formation method can reduce pollution of the photoresist layer and raises figure precision of the photoresist layer.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors, relate in particular to a kind of formation method of semiconductor structure.
Background technology
In the manufacture process of SIC (semiconductor integrated circuit), photoetching is a kind of for defining the conventional process in subsequent technique region.Described photoetching process comprises, first in semiconductor layer surface, forms photoresist layer (photoresist, PR); Then described photoresist layer is carried out to exposure imaging, make described photoresist layer graphical, and expose pending semiconductor layer surface; Afterwards exposed pending semiconductor layer is carried out to the subsequent techniques such as etching or Implantation.
Pending surface in existing technological process is often smooth not, and after photoresist layer is exposed, the interface that described photoresist layer contacts with pending surface can make incident light reflect, thus the pattern precision after impact exposure.Therefore, existing technique can form bottom layer anti-reflection layer (BARC, Bottom Anti-reflection Coat) on described pending surface before forming photoresist layer, and the incident light that is mapped to pending surface by absorption prevents reflection.
Existing photo-etching technological process please refer to Fig. 1 to Fig. 3, comprising:
Please refer to Fig. 1, Semiconductor substrate 100 is provided, described Semiconductor substrate 100 surfaces have device layer 101, the follow-up semiconductor devices that is used to form of described device layer 101, and the material of described device layer 101 is one or more in insulating material, Semiconductor substrate and metal material.
Please refer to Fig. 2, on described device layer 101 surfaces, form bottom anti-reflection layer 102, the material of described bottom anti-reflection layer 102 is organic material, ethyl orthosilicate for example, and the formation technique of described bottom anti-reflection layer 102 is spin coating proceeding.
Please refer to Fig. 3, on described bottom anti-reflection layer 102 surfaces, form photoresist layer 103.
Form after described photoresist layer 103, graphical to described photoresist layer 103 exposure imagings, expose pending device layer 101 surfaces; After exposure, bottom anti-reflection layer 102 and photoresist layer 103 described in thermal treatment.
Yet even formed bottom antireflective coating before forming photoresist layer, the figure degree of accuracy after described photoresist layer exposure is still poor.
More anti-reflecting layers please refer to the U.S. patent documents that the patent No. is US 7361455 B2.
Summary of the invention
The problem that the present invention solves is to provide a kind of formation method of semiconductor structure, reduces the pollution of photoresist layer, improves the pattern precision of photoresist layer.
For addressing the above problem, the invention provides a kind of formation method of semiconductor structure, comprising: Semiconductor substrate is provided, and described semiconductor substrate surface has device layer; On described device layer surface, form anti-reflection film, described anti-reflection film contains fluorinated polymer; Described anti-reflection film is carried out to thermal annealing, described anti-reflection film is formed and be positioned at first anti-reflecting layer on described device layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface; After thermal annealing, at described barrier layer surface, form photoresist layer, described photoresist layer defines the position that needs etching.
Alternatively, the material on restraining barrier contains fluorinated polymer.
Alternatively, the thickness on restraining barrier is 2 nanometer-10 nanometers.
Alternatively, the time of described thermal annealing is 30 seconds-300 seconds, and temperature is 120 degrees Celsius-300 degrees Celsius.
Alternatively, described fluorinated polymer is by poly-fluorinated acrylic ester, poly-fluorinated methyl acrylate, poly-homopolymer or the multipolymer of fluoridizing one or more formations in dioxolanes, teflon, polytetrafluoro oxirene and poly-difluoro oxirene.
Alternatively, the formation technique of described anti-reflection film is spin coating proceeding, and the thickness of described anti-reflection film is 150 dust-5000 dusts.
Alternatively, also comprise: described device layer surface has the second anti-reflecting layer, described the first anti-reflecting layer is positioned at described the second anti-reflecting layer surface.
Alternatively, the material of described the second anti-reflecting layer is silicon nitride or silicon oxynitride.
Alternatively, also comprise: between described the second anti-reflecting layer and device layer, have enhancement layer, the material of described enhancement layer is agraphitic carbon.
Alternatively, the material of described device layer is one or more combinations in insulating material, semiconductor material and metal material.
Alternatively, the material of described device layer comprises low-K dielectric material.
Alternatively, described anti-reflection film also comprises: polymer resin, crosslinking chemical, solvent and crosslinking catalyst.
Alternatively, described polymer resin is homopolymer or the multipolymer of one or more formations in poly-maleic anhydride, poly-dimethyl succinic acid, polyacrylate and polymethacrylate.
Alternatively, on the trunk of described polymer resin, there is crosslinking group, and the crosslinking group on the trunk of described polymer resin is connected with chromophoric group, etching strengthen group and affinity groups.
Alternatively, described chromophoric group comprises aromatic hydrocarbon.
Alternatively, described crosslinking chemical comprises one or more combinations in melamine methylol, alkoxymethyl melamine, Lauxite, benzyl ether, phenmethylol, epoxy compound, phenolics, isocyanide hydrochloric acid, acrylamide alkane and Methacrylamide.
Alternatively, described solvent comprises one or more combinations in butyrolactone, the third pentanone, cyclohexanone, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide, N methyl pyrrolidone, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, ethyl acetate.
Alternatively, the mass percent concentration of described solvent in anti-reflection film is 40 ~ 99.8%.
Alternatively, the forming process of described photoresist layer is: at described barrier layer surface spin coating photoresist film, and heat-treat; After thermal treatment, described photoresist film is carried out to exposure figure, expose the barrier layer surface that needs etching position, form photoresist layer; Described photoresist layer is heat-treated.
Compared with prior art, technical scheme of the present invention has the following advantages:
Make the anti-reflection film that is formed at device layer surface contain fluorinated polymer, in the process of anti-reflection film described in thermal treatment, described fluorinated polymer accumulates in described fluorinated polymer surface owing to being subject to the effect of the power of being separated, thereby after thermal treatment, can form and be positioned at first anti-reflecting layer on described device layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface, described restraining barrier comprise fluorinated polymer; Because described restraining barrier is fine and close, can, in the process of follow-up formation photoresist layer, prevent that ion or the gas molecule in described device layer from passing described the first anti-reflecting layer and diffusing into photoresist layer, thereby avoid described photoresist layer to be out of shape because being subject to polluting; Improved the precision of formed photoresist layer, made the characteristic dimension of follow-up formed semiconductor devices more easy to control; And, only need to form one deck anti-reflection film and thermal annealing can form restraining barrier, reach the object that prevents that photoresist from polluting, can conservation, simplify processing step, thus cost-saving; In addition, adopt described anti-reflection film, reduce the restriction that the material of device layer is selected, can be widely used.
Accompanying drawing explanation
Fig. 1 to Fig. 3 is the cross-sectional view of existing photo-etching technological process;
Fig. 4 is the schematic flow sheet of formation method first embodiment of semiconductor structure of the present invention;
Fig. 5 to Fig. 9 is the cross-sectional view of forming process first embodiment of semiconductor structure of the present invention;
Figure 10 is the schematic flow sheet of formation method second embodiment of semiconductor structure of the present invention;
Figure 11 to Figure 14 is the cross-sectional view of forming process second embodiment of semiconductor structure of the present invention.
Embodiment
As stated in the Background Art, even formed bottom antireflecting coating before forming photoresist layer, the figure degree of accuracy after described photoresist layer exposure is still poor.
Along with reducing of features in semiconductor devices chi, the raising of precision, the lambda1-wavelength in photoetching process is corresponding reducing also, to improve the resolution of photoetching process; Yet incident light wavelength is shorter, more easily reflects; Therefore, prior art is in order to improve antireflecting effect, at described device layer 101(as shown in Figure 2) and bottom anti-reflection layer 102(as shown in Figure 2) between form again one deck medium anti-reflecting layer (DARC, Dielectric Anti-reflection Coat), the material of described medium anti-reflecting layer is silicon nitride or silicon oxynitride.
The present inventor finds through research, owing to containing nitrogen ion in described medium anti-reflecting layer, please refer to Fig. 3, in the process at bottom anti-reflection layer described in thermal treatment 102 and photoresist layer 103, described medium anti-reflecting layer can produce ammonia, described ammonia can pass bottom anti-reflection layer 102, and diffuses into described photoresist layer 103; Because described photoresist layer 103 is acid, and ammonia is alkalescence, and chemical reaction can occur for both, causes the figure of photoresist layer to change, and has reduced the degree of accuracy of photoresist layer.
In addition,, please continue to refer to Fig. 3, if when described device layer 101 is low-K material, owing to having more defect in described low-K material, described defect can trapping ion or gas molecule, for example nitrogen of Chang Zuowei carrier gas or reacting gas in semiconductor processes; When bottom anti-reflection layer described in thermal treatment 102 and photoresist layer 103, the ion of capturing or gas molecule can pass bottom anti-reflection layer 102, and diffuse in photoresist layer 103, cause the figure deformation of photoresist layer 103, reduced the degree of accuracy of photoresist layer 103.
Through the present inventor, further study discovery, in described bottom anti-reflection layer, add fluorinated polymer, and after bottom anti-reflection layer described in spin coating, then heat-treat; Described bottom anti-reflection layer, owing to being subject to the impact of the power of being separated (Phase Separate Force), can be isolated the restraining barrier that is positioned at described bottom anti-reflection layer surface; And described restraining barrier is fine and close, can stop the ammonia being discharged by medium anti-reflecting layer, or the ion of capturing in low K dielectric layer or gas molecule; Avoided the pollution of photoresist layer, made the degree of accuracy of formed photoresist layer higher, made the characteristic dimension of formed semiconductor devices more easy to control; And, only need to form one deck bottom anti-reflection layer and can reach the object that prevents that photoresist from polluting, can be cost-saving; In addition, adopt described bottom anti-reflection layer, reduce the restriction that the material of device layer is selected, can be widely used.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.
The first embodiment
Fig. 4 is the schematic flow sheet of formation method first embodiment of semiconductor structure of the present invention, comprising:
Step S101, provides Semiconductor substrate, and described semiconductor substrate surface has device layer;
Step S102, forms the second anti-reflecting layer on described device layer surface, and the material of described the second anti-reflecting layer is silicon nitride or silicon oxynitride;
Step S103, forms anti-reflection film on described the second anti-reflecting layer surface, and described anti-reflection film contains fluorinated polymer;
Step S104, carries out thermal annealing to described anti-reflection film, described anti-reflection film is formed and be positioned at first anti-reflecting layer on described the second anti-reflecting layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface;
Step S105, after thermal annealing, forms photoresist layer at described barrier layer surface, and described photoresist layer defines the position that needs etching.
Below with reference to accompanying drawing, formation method first embodiment of semiconductor structure of the present invention is described, Fig. 5 to Fig. 9 is the cross-sectional view of forming process first embodiment of semiconductor structure of the present invention.
Please refer to Fig. 5, Semiconductor substrate 200 is provided, described Semiconductor substrate 200 surfaces have device layer 201.
Described Semiconductor substrate 200 is used to subsequent technique that workbench is provided, and the material of described Semiconductor substrate 200 is silicon, SiGe, silit, silicon-on-insulator or III-V compounds of group (such as silicon nitride or gallium arsenide etc.).
Described device layer 201 is for forming a part for semiconductor devices or device at subsequent technique, the material of described device layer 201 comprises: one or more combinations in insulating material, semiconductor material and metal material; The material of described device layer, formation technique or size are determined according to concrete technology, at this, should too not limit; In the present embodiment, the material of described device layer 201 is monox.
Please refer to Fig. 6, on described device layer 201 surfaces, form the second anti-reflecting layer 202, the material of described the second anti-reflecting layer 202 is silicon nitride or silicon oxynitride.
The formation technique of described the second anti-reflecting layer 202 is depositing operation, preferably chemical vapor deposition method; Described the second anti-reflecting layer 202 is medium anti-reflecting layer, by regulating the nitrogen content in described the second anti-reflecting layer 202, can control the absorption coefficient of light of described the second anti-reflecting layer 202; In the present embodiment, described the second anti-reflecting layer 202, with subsequent technique in the first anti-reflecting layer of forming, follow-up, when photoresist layer expose, jointly prevent that incident light is in described device layer 201 surface generation diffuse reflections; Further avoided making photoresist layer figure deformation because of incident light reflection.
It should be noted that, in other embodiments, before forming described the second anti-reflecting layer 202, on described device layer 201 surfaces, form enhancement layer (not shown); Described enhancement layer is for strengthening graphic films (APF, Advanced Patterning Film), and material is agraphitic carbon, for further strengthening anti-reflection effect; While in addition, removing described the second anti-reflecting layer 202 due to subsequent technique, can cause damage to described device layer; And between described enhancement layer and the material of device layer, there is larger Etch selectivity, thereby during the enhancement layer on etching removal devices layer surface, less to the damage of described device layer.
Please refer to Fig. 7, on described the second anti-reflecting layer 202 surfaces, form anti-reflection film 203, described anti-reflection film 203 contains fluorinated polymer.
Described anti-reflection film 203 is used to form the first anti-reflecting layer and restraining barrier, and the material of described anti-reflection film 203 is organic material, and therefore the formation technique of described anti-reflection film 203 is spin coating proceeding, and the thickness of described anti-reflection film is 150 dust-5000 dusts.
In described anti-reflection film 203, contain fluorinated polymer, when subsequent thermal is annealed described anti-reflection film 203, described fluorinated polymer accumulates in described anti-reflection film 203 surfaces owing to being subject to the impact of the power of being separated, and forms the restraining barrier of one deck density; Described restraining barrier is used for isolating photoresist layer and first anti-reflecting layer of follow-up formation, thereby has avoided the pollution of photoresist layer, makes photoresist layer figure accurate.
In the present embodiment, described fluorinated polymer is poly-fluorinated acrylic ester, and poly-fluorinated methyl acrylate, gathers and fluoridize dioxolanes, teflon, one or more homopolymer that constitute or multipolymer in polytetrafluoro oxirene and poly-difluoro oxirene.
The material of described anti-reflection film 203, except fluorinated polymers beyond the region of objective existence, also comprises: polymer resin, crosslinking chemical, solvent, and crosslinking catalyst; Wherein, described polymer resin is one or more homopolymer that form or the multipolymer in poly-maleic anhydride, poly-dimethyl succinic acid, polyacrylate and polymethacrylate; On the trunk of described polymer resin, there is crosslinking group, and on the trunk of described polymer resin, connect chromophoric group, etching strengthen group and affinity groups; Wherein, described chromophoric group consists of aromatic hydrocarbon, for example aromatic hydrocarbon of the many benzene based on anthracene, or the single benzene aromatic hydrocarbon based on benzene; Or if described polymer resin is not connected with chromophoric group, described polymer resin can mix with dye monomer.
In addition, the crosslinking chemical in described anti-reflection film 203 is for crosslinked organism group, and described crosslinking chemical contains one or more in hydroxyl, amide group, carboxyl and mercapto; In the present embodiment, described crosslinking chemical comprises: one or more mixing in melamine methylol, alkoxymethyl melamine, Lauxite, benzyl ether, phenmethylol, epoxy compound, phenolics, isocyanide hydrochloric acid, acrylamide alkane, Methacrylamide.
Described solvent can dissolve each organic material in described anti-reflection film 203, and forms stable organic solution, and is the organism that toxicity is less; Described solvent is one or more mixing in butyrolactone, the third pentanone, cyclohexanone, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide, N methyl pyrrolidone, propylene glycol monomethyl ether (PGME), 1-Methoxy-2-propyl acetate (PGMEA), ethyl acetate; In the present embodiment, described solvent is mixed and is formed by 1-Methoxy-2-propyl acetate and ethyl acetate; The mass percent concentration of described solvent in anti-reflection film 203 is 40 ~ 99.8%.
Please refer to Fig. 8, to described anti-reflection film 203(as shown in Figure 7) carry out thermal annealing, described anti-reflection film forms the first anti-reflecting layer 203a that is positioned at described the second anti-reflecting layer 202 surfaces, and the restraining barrier 203b that is positioned at described the first anti-reflecting layer 203a surface.
The time of described thermal annealing is 30 seconds-300 seconds, and temperature is 120 degrees Celsius-300 degrees Celsius; In the process of thermal annealing, the fluorinated polymer in described anti-reflection film 203 is subject to the impact of the power of being separated and moves to described anti-reflection film 203 surfaces, and gathers on described anti-reflection film 203 surfaces; Thereby after thermal annealing, described anti-reflection film 203 is separated into: be positioned at the first anti-reflecting layer 203a on the second anti-reflecting layer 202 surfaces, and the restraining barrier 203b that contains fluorinated polymer.
The thickness of described restraining barrier 203b is 2 nanometer-10 nanometers; Because described restraining barrier 203b is fine and close, therefore can the heat treatment process after post-exposure photoresist layer in, stop that the ammonia that described the second anti-reflecting layer 202 produces enters photoresist layer; In addition, because described restraining barrier 203b contains fluorinated polymer, be acid, can neutralize the ammonia that is alkaline, its blocking effect is better, has avoided the pollution to photoresist layer, and formed photoresist layer figure is more easy to control, and degree of accuracy is higher; In addition, described restraining barrier 203b is without on the basis of existing processing step, and extra adding technology step can form, thereby has simplified technique, has saved cost.
Described the first anti-reflecting layer 203a is bottom anti-reflection layer, at subsequent optical carving technology, prevents that incident light from affecting the degree of accuracy of formed photoresist layer figure in device layer 201 surface generation reflections.
Please refer to Fig. 9, after thermal annealing, on described restraining barrier 203b surface, form photoresist layer 204, described photoresist layer 204 defines the position that needs etching.
The forming process of described photoresist layer 204 is: at described restraining barrier 203b surface spin coating photoresist film (not shown), and carry out thermal treatment for the first time; After thermal treatment for the first time, described photoresist film is carried out to exposure figure, expose the barrier layer surface that needs etching position, form photoresist layer; After exposure, described photoresist layer is carried out to the second thermal treatment.
Because the material of described the second anti-reflecting layer 202 is silicon nitride or silicon oxynitride, in thermal treatment for the first time with for the second time in heat treated process, described the second anti-reflecting layer 202 can discharge ammonia, and described ammonia can pass the first anti-reflecting layer 203a; If described ammonia contacts with photoresist layer 204, because described photoresist layer 204 is acid, and described ammonia is alkalescence, and ammonia can react with photoresist layer 204, the figure of described photoresist layer 204 is deformed, thereby reduced the degree of accuracy of photoresist layer 204 figures.
In the present embodiment, the ammonia that the second anti-reflecting layer 202 discharges is through after the first anti-reflecting layer 203a, and 203b contacts with restraining barrier; Because described restraining barrier 203b is fine and close, can stop that ammonia molecule passes, thereby prevent the pollution of ammonia to photoresist layer 204; In addition, because described restraining barrier 203b consists of fluorinated polymer, be acid, therefore can consume the ammonia of contact with it, improved the effect stopping; Make the figure of described photoresist layer 204 more easy to control, degree of accuracy improves.
The formation method of semiconductor structure described in the present embodiment, can form restraining barrier 203b at the second anti-reflecting layer 202 and the first anti-reflecting layer 203a surface, described restraining barrier 203b can, in forming the process of photoresist layer 204, prevent that the ammonia that described the second anti-reflecting layer 202 discharges from polluting described photoresist layer 204; Formed photoresist layer 204 figures are more easy to control, and degree of accuracy is higher, make the characteristic dimension of semiconductor devices of follow-up formation more easy to control; In addition, described restraining barrier 203b and the first anti-reflecting layer 203a form simultaneously, without adding extra processing step, have simplified technique, cost-saving.
The second embodiment
Figure 10 is the schematic flow sheet of formation method second embodiment of semiconductor structure of the present invention, comprising:
Step S201, provides Semiconductor substrate, and described semiconductor substrate surface has device layer, and described device layer comprises low K dielectric layer;
Step S202, forms anti-reflection film on described device layer surface, and described anti-reflection film contains fluorinated polymer;
Step S203, carries out thermal annealing to described anti-reflection film, described anti-reflection film is formed and be positioned at first anti-reflecting layer on described device layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface;
Step S204, after thermal annealing, forms photoresist layer at described barrier layer surface, and described photoresist layer defines the position that needs etching.
Below with reference to accompanying drawing, formation method second embodiment of semiconductor structure of the present invention is described, Figure 11 to Figure 14 is the cross-sectional view of forming process second embodiment of semiconductor structure of the present invention.
Please refer to Figure 11, Semiconductor substrate 300 is provided, described Semiconductor substrate 300 surfaces have device layer (not shown), and described device layer comprises low K dielectric layer 302.
Described Semiconductor substrate 300 is used to subsequent technique that workbench is provided, and the material of described Semiconductor substrate 300 is silicon, SiGe, silit, silicon-on-insulator or III-V compounds of group (such as silicon nitride or gallium arsenide etc.).
The device layer of the present embodiment is used to form damascene structure, described device layer comprises: be positioned at described Semiconductor substrate 300 surfaces metal level 301, be positioned at the low K dielectric layer 302 on described metal level 301 surfaces and the mask layer 303 that is positioned at described low K dielectric layer 302 surfaces, in described mask layer 303 and low K dielectric layer 302, have two grooves 304 of isolation mutually, described groove 304 exposes described metal level 301 surfaces; The formation technique of described device layer is well known to those skilled in the art, and at this, does not repeat.
In described low K dielectric layer 302, there is more defect, trapping ion or gas molecule in described defect Hui Ge road technological process, the especially nitrogen of Chang Zuowei carrier gas or reacting gas in semiconductor processes; In the process of follow-up formation photoresist layer, described ion or gas molecule easily diffuse into photoresist layer, cause described photoresist layer distortion.
Please refer to Figure 12, at described groove 304(as shown in figure 12) in and mask layer 303 surface form anti-reflection films 305, described anti-reflection film 305 contains fluorinated polymer.
The material of described anti-reflection film 305 is organic material, and formation technique is spin coating proceeding, and thickness is 150 dust-5000 dusts; Described anti-reflection film 305 is for forming the first anti-reflecting layer and restraining barrier at subsequent technique.
In described anti-reflection film 305, contain fluorinated polymer, in follow-up thermal annealing process, described fluorinated polymer is mobile to described anti-reflection film 305 surfaces due to the impact of the power of being separated; After thermal annealing, described fluorinated polymer accumulates in described anti-reflection film 305 surfaces, and forms the restraining barrier of one deck density, for isolating photoresist layer and first anti-reflecting layer of follow-up formation, thereby avoided the pollution of photoresist layer, made photoresist layer figure accurate.
In the present embodiment, described fluorinated polymer is poly-fluorinated acrylic ester, and poly-fluorinated methyl acrylate, gathers and fluoridize dioxolanes, teflon, one or more homopolymer that constitute or multipolymer in polytetrafluoro oxirene and poly-difluoro oxirene.
The material of described anti-reflection film 305, except fluorinated polymers beyond the region of objective existence, also comprises: polymer resin, crosslinking chemical, solvent, and crosslinking catalyst; The concrete material of described anti-reflection film is identical with the first embodiment, and therefore not to repeat here.
Please refer to Figure 13, to described anti-reflection film 305(as shown in figure 13) carry out thermal annealing, described anti-reflection film 305 forms and is positioned at described groove 304(as shown in figure 12) and the first anti-reflecting layer 305a on mask layer 303 surfaces, and the restraining barrier 305b that is positioned at described the first anti-reflecting layer 305a surface.
The time of described thermal annealing is 30 seconds-300 seconds, and temperature is 120 degrees Celsius-300 degrees Celsius; In the process of thermal annealing, the fluorinated polymer in described anti-reflection film 305 is subject to the impact of the power of being separated and moves to described anti-reflection film 305 surfaces, and gathers on described anti-reflection film 305 surfaces; Therefore, after thermal annealing, described anti-reflection film 305 is separated into the first anti-reflecting layer 305a that is positioned at groove 304 and mask layer 303 surfaces, and is positioned at described the first anti-reflecting layer 305a surface, the restraining barrier 305b that contains fluorinated polymer.
The thickness of described restraining barrier 305b is 2-10 nanometer; Because described restraining barrier 305b is fine and close, therefore can the heat treatment process after post-exposure photoresist layer in, prevent that ion or the gas molecule in described low K dielectric layer 302 defects from diffusing in photoresist layer; In addition, described restraining barrier 305b is without on the basis of existing processing step, and extra adding technology step can form, thereby has simplified technique, has saved cost.
Described the first anti-reflecting layer 305a is bottom anti-reflection layer, at subsequent optical carving technology, prevents that incident light is in sidewall and the bottom of groove 304, and mask layer 303 surface reflection occurs and affects the degree of accuracy of formed photoresist layer figure.
Please refer to Figure 14, after thermal annealing, on described restraining barrier 305b surface, form photoresist layer 306, described photoresist layer 306 defines and needs the position of etching and heat-treat.
The forming process of described photoresist layer 306 is: at described restraining barrier 305b surface spin coating photoresist film (not shown), and carry out thermal treatment for the first time; After thermal treatment for the first time, described photoresist film is carried out to exposure figure, expose the barrier layer surface that needs etching position, form photoresist layer; After exposure, described photoresist layer is carried out to the second thermal treatment.
Owing to thering is defect in described low K dielectric layer, and trapping ion or gas molecule in the easy Ge of described defect road semiconductor fabrication process, be especially usually used in technique the nitrogen as carrier gas or reacting gas; In described thermal treatment for the first time and for the second time in heat treated process, described defect intermediate ion or gas molecule are subject to heat and drive, can move to described the first anti-reflecting layer 305a, and described ion or gas molecule are less, easily pass described the first anti-reflecting layer 305a and diffuse into photoresist layer 306, cause the figure of photoresist layer 306 to deform, reduced the degree of accuracy of photoresist layer 306 figures, affect the characteristic dimension of formed semiconductor devices.
In the present embodiment, the ion in the defect of described low K dielectric layer 302 or gas molecule, for example nitrogen, passes after described the first anti-reflecting layer 305a, and 305b contacts with restraining barrier; Because described restraining barrier 305b is fine and close, can stop that nitrogen molecule passes, avoided the pollution of nitrogen to photoresist layer 204; The figure of photoresist layer 306 is more easy to control, and degree of accuracy improves.
Described in the present embodiment in the formation method of semiconductor structure, because the low K dielectric layer in described device layer has defect, easily trapping ion or gas molecule; On the first anti-reflecting layer 305a surface, form restraining barrier 305b; Because described restraining barrier 305b is fine and close, in the forming process of photoresist layer 306, described restraining barrier 305b can prevent that ion or the gas molecule in low K dielectric layer 302 from diffusing into photoresist layer 306; Formed photoresist layer 306 figures are more easy to control, and degree of accuracy is higher, make the characteristic dimension of semiconductor devices of follow-up formation more easy to control; In addition, described restraining barrier 305b and the first anti-reflecting layer 305a form simultaneously, without adding extra processing step, have simplified technique, cost-saving; Again, because described anti-reflection film 305 can form restraining barrier 305b, the corresponding reduction of restriction that the material of device layer is selected, described anti-reflection film 305 can be widely used.
In sum, make the anti-reflection film that is formed at device layer surface contain fluorinated polymer, in the process of anti-reflection film described in thermal treatment, described fluorinated polymer accumulates in described fluorinated polymer surface owing to being subject to the effect of the power of being separated, thereby after thermal treatment, can form and be positioned at first anti-reflecting layer on described device layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface, described restraining barrier comprise fluorinated polymer; Because described restraining barrier is fine and close, can, in the process of follow-up formation photoresist layer, prevent that ion or the gas molecule in described device layer from passing described the first anti-reflecting layer and diffusing into photoresist layer, thereby avoid described photoresist layer to be out of shape because being subject to polluting; Improved the precision of formed photoresist layer, made the characteristic dimension of follow-up formed semiconductor devices more easy to control; And, only need to form one deck anti-reflection film and thermal annealing can form restraining barrier, reach the object that prevents that photoresist from polluting, can conservation, simplify processing step, thus cost-saving; In addition, adopt described anti-reflection film, reduce the restriction that the material of device layer is selected, can be widely used.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; can utilize method and the technology contents of above-mentioned announcement to make possible change and modification to technical solution of the present invention; therefore; every content that does not depart from technical solution of the present invention; any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, all belong to the protection domain of technical solution of the present invention.
Claims (19)
1. a formation method for semiconductor structure, is characterized in that, comprising:
Semiconductor substrate is provided, and described semiconductor substrate surface has device layer;
On described device layer surface, form anti-reflection film, described anti-reflection film contains fluorinated polymer;
Described anti-reflection film is carried out to thermal annealing, described anti-reflection film is formed and be positioned at first anti-reflecting layer on described device layer surface and the restraining barrier that is positioned at described the first anti-reflecting layer surface;
After thermal annealing, at described barrier layer surface, form photoresist layer, described photoresist layer defines the position that needs etching.
2. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, the material on restraining barrier contains fluorinated polymer.
3. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, the thickness on restraining barrier is 2 nanometer-10 nanometers.
4. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, the time of described thermal annealing is 30 seconds-300 seconds, and temperature is 120 degrees Celsius-300 degrees Celsius.
5. the formation method of semiconductor structure as claimed in claim 1, it is characterized in that, described fluorinated polymer is by poly-fluorinated acrylic ester, poly-fluorinated methyl acrylate, gathers and fluoridize one or more homopolymer that form or the multipolymer in dioxolanes, teflon, polytetrafluoro oxirene and poly-difluoro oxirene.
6. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, the formation technique of described anti-reflection film is spin coating proceeding, and the thickness of described anti-reflection film is 150 dust-5000 dusts.
7. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, also comprises: described device layer surface has the second anti-reflecting layer, and described the first anti-reflecting layer is positioned at described the second anti-reflecting layer surface.
8. the formation method of semiconductor structure as claimed in claim 7, is characterized in that, the material of described the second anti-reflecting layer is silicon nitride or silicon oxynitride.
9. the formation method of semiconductor structure as claimed in claim 7, is characterized in that, also comprises: between described the second anti-reflecting layer and device layer, form enhancement layer, the material of described enhancement layer is agraphitic carbon.
10. the formation method of semiconductor structure as claimed in claim 1, is characterized in that, the material of described device layer is one or more combinations in insulating material, semiconductor material and metal material.
The 11. formation methods of semiconductor structure as claimed in claim 10, is characterized in that, the material of described device layer comprises low-K dielectric material.
The 12. formation methods of semiconductor structure as claimed in claim 1, is characterized in that, described anti-reflection film also comprises: polymer resin, crosslinking chemical, solvent and crosslinking catalyst.
The 13. formation methods of semiconductor structure as claimed in claim 12, is characterized in that, described polymer resin is homopolymer or the multipolymer of one or more formations in poly-maleic anhydride, poly-dimethyl succinic acid, polyacrylate and polymethacrylate.
The 14. formation methods of semiconductor structure as claimed in claim 12, it is characterized in that having crosslinking group on the trunk of described polymer resin, and the crosslinking group on the trunk of described polymer resin are connected with chromophoric group, etching strengthen group and affinity groups.
The 15. formation methods of semiconductor structure as claimed in claim 14, is characterized in that, described chromophoric group comprises aromatic hydrocarbon.
The 16. formation methods of semiconductor structure as claimed in claim 12, it is characterized in that, described crosslinking chemical comprises one or more combinations in melamine methylol, alkoxymethyl melamine, Lauxite, benzyl ether, phenmethylol, epoxy compound, phenolics, isocyanide hydrochloric acid, acrylamide alkane and Methacrylamide.
The 17. formation methods of semiconductor structure as claimed in claim 12, it is characterized in that, described solvent comprises one or more combinations in butyrolactone, the third pentanone, cyclohexanone, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide, N methyl pyrrolidone, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, ethyl acetate.
The 18. formation methods of semiconductor structure as claimed in claim 12, is characterized in that, the mass percent concentration of described solvent in anti-reflection film is 40 ~ 99.8%.
The 19. formation methods of semiconductor structure as claimed in claim 1, is characterized in that, the forming process of described photoresist layer is: at described barrier layer surface spin coating photoresist film, and heat-treat; After thermal treatment, described photoresist film is carried out to exposure figure, expose the barrier layer surface that needs etching position, form photoresist layer; Described photoresist layer is heat-treated.
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