CN107390471A - One kind is used for resist and its application of two-photon photoetching - Google Patents
One kind is used for resist and its application of two-photon photoetching Download PDFInfo
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- CN107390471A CN107390471A CN201710719138.0A CN201710719138A CN107390471A CN 107390471 A CN107390471 A CN 107390471A CN 201710719138 A CN201710719138 A CN 201710719138A CN 107390471 A CN107390471 A CN 107390471A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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Abstract
The present invention relates to a kind of resist for being used for two-photon photoetching and its application, belong to technical field of micro and nano fabrication, the resist includes component A and component B；According to the mass fraction, the component A includes 100 parts of cage-type silsesquioxane compound, 0.1 5 parts of two-photon sensitising agent, 0.1 5 parts of light trigger, 15 parts of auxiliary agent；The component B is 5 95% solvent based on the component A gross masses.The resist has nonlinear optical effect, excellent dielectricity and heat endurance, is resistant to 350 DEG C of high temperature above, can carry out wet etching or CHF by HF solution3, oxygen plasma dry etching；Class silicon dioxide structure C is converted into after 500 DEG C of high temperature above sinteringxSiOy, such silicon dioxide structure CxSiOyWet etching or CHF can also be carried out by HF solution3, oxygen plasma dry etching.Resist in the present invention can perform well in alternative gate processing, and satisfaction is enclosed in gate nano line device fabrication process, the physical and chemical performance requirement of two-photon process technology and semiconductor technology for alternative gate resist.
Description
Technical field
The invention belongs to technical field of micro and nano fabrication, and in particular to one kind is used for the resist of two-photon photoetching and its answered
With.
Background technology
In the today in " rear mole of epoch ", Development of Novel three-D micro-nano information apparatus will be break through Moore's Law possibility way
One of footpath.Peking University's Huang such as academician proposes autoregistration and encloses gate nano line device to tackle Moore's Law challenge.Enclose grid nanometer
The key that line device moves towards large-scale integrated application is the integrated compatibility of technique, and being related to technique includes：Resist replaces
For steps such as grid processing, the removal of plasma CVD deposited silicon nitride, alternative gate, gate material backfills.Due to hanging silicon nanowires
Shadowing effect, conventional lithographic techniques, the energy source of electron beam lithography can not reach shaded areas below silicon nanowires, no
Effective exposure of alternative gate structure can be realized.Chinese Academy of Sciences's section declare researcher propose using photon diffraction through characteristic and
Various dimensions control ability, to solve the 3 D stereo exposure technique difficult point in the case of masking grating.Simulation results show：It is more
Photon process technology can evade the shadowing effect that hanging silicon nanowires is brought, and realize the controllable processing of alternative gate, still, multi-photon
It is claimed below that process technology and semiconductor technology require that the physical and chemical performance of alternative gate resist meets simultaneously：(1) resist is non-thread
Property optical effect be realize nano-precision, nanoscale and three-dimensional structure processing basis；(2) low-temperature plasma CVD deposition
Technological requirement alternative gate has higher heat endurance (long-term use of temperature>350℃)；(3) hydrofluoric acid (HF) is to alternative gate material
Material and silicon nitride have selective etching；(4) standard semi-conductor processes require substitute grid material have excellent dielectric properties and
It is pollution-free.However, the resist of commercialization at present there is no method while meet the condition of above-mentioned resist, therefore, it is badly in need of a kind of use
In the anticorrosive additive material of two-photon processing, to meet the requirement of femtosecond laser process technology.
The content of the invention
In view of this, it is an object of the invention to：(1) a kind of resist for being used for two-photon photoetching is provided；(2) one is provided
Class is used for the application of the resist of two-photon photoetching.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1st, a kind of resist for being used for two-photon photoetching, it is characterised in that the resist includes component A and component B；Press
Mass fraction meter, the component A include 100 parts of cage-type silsesquioxane compound, and two-photon sensitising agent 0.1-5 parts are light-initiated
Agent 0.1-5 parts, auxiliary agent 1-5 parts；The component B is the solvent of the 5-95% based on the component A gross masses；The cage model sesquialter
The chemical formula of silicone compounds is Rm(SiO1.5)8, m is 2-8 positive integer, R structure such as any one of formula I-VI institute in formula
Show：
N is positive integer in formula I-VI.
Further, when R structure is formula I or II in the cage-type silsesquioxane compound, the light trigger is
One kind in crack type photoinitiator or hydrogen-capture-type light initiator；Preferably, the light trigger is benzoin and derivative, benzene
One kind in even acyl class, alkylbenzene ketone, acyl group phosphorous oxides, benzophenone or thioxanthones；It is furthermore preferred that the light
Initiator is styrax, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α,
Alpha, alpha-dimethyl epoxide-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine
Oxide, bis(benzoylphenyl) phosphine oxide, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton, thio propoxyl group thia
One kind in anthrone or isopropyl thioxanthone.
Further, when R structure is general formula III or IV in the cage-type silsesquioxane compound, the light trigger is
Cationic photoinitiator；Preferably, the light trigger is diaryl group iodized salt, triaryl salt compounded of iodine or isopropylbenzene cyclopentadienyl iron six
One kind in fluorophosphate.
Further, when R structure is formula V or VI in the cage-type silsesquioxane compound, the light trigger is
Crack type photoinitiator；Preferably, the light trigger is benzoin and derivative, benzil class, alkylbenzene ketone or acyl group
One kind in phosphorous oxides；It is furthermore preferred that the light trigger is styrax, benzoin dimethylether, benzoin ethyl ether, styrax
Isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone, α, α-diethoxy acetophenone, α-
One kind in hydroxyalkyl phenones, α-amine alkyl phenones, aroyl phosphine oxide or bis(benzoylphenyl) phosphine oxide.
Further, the two-photon sensitising agent is super phthalein green grass or young crops, dark green, ferroheme, chlorophyll, vitamin B2, methylene
One kind in blue or rhodamine B.
Further, the auxiliary agent is surfactant, storage stabilizing agent, defoamer, crosslinking agent, adhesion promoter or stream
One or more in flat agent.
Further, the solvent is one kind in propylene glycol methyl ether acetate, ethanol, isopropanol or acetone.
2nd, application of the described resist in three-D micro-nano information apparatus are manufactured.
Further, the three-D micro-nano information apparatus are to enclose gate nano line device.
The beneficial effects of the present invention are：The invention provides a kind of resist for being used for two-photon photoetching and its application,
Contain cage-type silsesquioxane compound in the resist, its structural formula is as shown in figure 1, the compound having for molecule level
Machine/inorganic hybrid material, cage modle SiO on skeleton1.5Physical dimension is 1-3nm, in heat endurance, dielectricity, mechanical strength, anti-
There is class SiO in etching property2Characteristic, by introducing feature functional group, it is high anti-that cage-type silsesquioxane nano-particle can be assigned
Should be active, for micro-nano technology.Meanwhile by adding two-photon sensitising agent, light trigger, auxiliary agent etc., make finally to prepare resists
Erosion agent has nonlinear optical effect, and when enclosing grid nano-device using the manufacture of two-photon resist, energy source can reach silicon
Shaded areas below nano wire, so as to realize effective exposure of alternative gate structure, and the resist is formed after two-photon is processed
Micro-nano structure 350 DEG C of high temperature above are resistant in air and inert gas shielding atmosphere, the micro-nano structure can be molten by HF
Liquid carries out wet etching or CHF3, oxygen plasma dry etching.Further, what the resist was formed after two-photon is processed is micro-
Micro-nano structure is converted into class silicon dioxide structure C after 500 DEG C of high temperature above sinterxSiOy, such silicon dioxide structure CxSiOy
Wet etching or CHF can be carried out by HF solution3, oxygen plasma dry etching.In summary, the resist in the present invention
Alternative gate processing can be performed well in, satisfaction is enclosed in gate nano line device fabrication process, two-photon process technology and semiconductor
Physical and chemical performance requirement of the technique for alternative gate resist.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the structural representation of cage-type silsesquioxane compound in two-photon resist in the present invention；
Fig. 2 is the thermogravimetric curve of the two-photon resist prepared in embodiment 8；
Fig. 3 is the spin coating curve of the two-photon resist prepared in embodiment 8；
Fig. 4 is the infrared spectrogram of the two-photon resist prepared in embodiment 8；
Fig. 5 is the X diffraction light electronic energy spectrums of the two-photon resist prepared in embodiment 8；
Fig. 6 is the mask plate that the resolution ratio made by the two-photon resist prepared in UVA exposure embodiments 8 is 2um
Graphic structure；
Fig. 7 is the three-dimensional yard structure made by the two-photon resist prepared in two-photon Lithographic Example 8；
Fig. 8 is the network made by the two-photon resist prepared in two-photon Lithographic Example 8 at 500 DEG C
Graphic structure of the sintering before and after 1 hour.
Fig. 9 is the process chart that grid nano-device is enclosed with the two-photon resist manufacture prepared in embodiment 8.
Embodiment
The preferred embodiments of the present invention will be described in detail below.
Embodiment 1
Weigh 100 parts of propyl methacrylate cage-type silsesquioxane ((C7H11O2)m(SiO1.5)8, wherein m=2), 0.1
The super phthalein of part is blue or green, 0.1 part of thio propoxyl group thioxanthone, the mixture of 1 part of surfactant, storage stabilizing agent and defoamer, with
Propylene glycol methyl ether acetate is solvent, and solvent quality is the 5% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in the third two
920nm is made in alcohol methyl ether acetate, after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 2
Weigh 100 parts of propyl methacrylate cage-type silsesquioxane ((C7H11O2)m(SiO1.5)8, wherein m=5), 0.2
Part ferroheme, 0.2 part of α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone, the mixture of 2 parts of surfactants, crosslinking agent and defoamer,
Using isopropanol as solvent, solvent quality is the 10% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, filled
570nm absorption radical polymerization mould assembly two-photon resists are made after dividing mixing.
Embodiment 3
Weigh 100 parts of propyl methacrylate cage-type silsesquioxane ((C7H11O2)m(SiO1.5)8, wherein m=8), 3 parts
Vitamin B2,3 parts of benzoin isopropyl ethers, 1.5 parts of crosslinking agents, attachment are made every effort to promote, the mixture of storage stabilizing agent and defoamer, with second
Alcohol is solvent, and solvent quality is the 15% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in ethanol, after being sufficiently mixed
440nm is made and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 4
Weigh 100 parts of propyl acrylate cage-type silsesquioxane ((C6H9O2)m(SiO1.5)8, wherein m=2), 0.5 part of Luo Dan
Bright B, 0.5 part of α-amine alkyl phenones, the mixture of 2 parts of surfactants, storage stabilizing agent and levelling agent, using acetone as solvent,
Solvent quality is the 20% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in acetone, 550nm is made after being sufficiently mixed
Absorb radical polymerization mould assembly two-photon resist.
Embodiment 5
Weigh 100 parts of first propyl acrylate cage-type silsesquioxane ((C6H9O2)m(SiO1.5)8, wherein m=4), 2.5 parts of Asias
Methyl blue, 2.5 parts of bis(benzoylphenyl) phosphine oxides, 2.5 parts of surfactants, adhesion promoter, levelling agent and defoamer
Mixture, using ethanol as solvent, solvent quality be above-mentioned each component quality summation 25%.Above-mentioned each component is dissolved in ethanol
In, 650nm is made after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 6
Weigh 100 parts of propyl acrylate cage-type silsesquioxane ((C6H9O2)m(SiO1.5)8, wherein m=6), 4 parts of leaves are green
Element, 4 parts of 2,4-DihydroxyBenzophenones, the mixture of 3 parts of surfactants, storage stabilizing agent and defoamer, with propane diols first
Ether acetate is solvent, and solvent quality is the 30% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in propylene glycol monomethyl ether
456nm is made in acetate, after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 7
Weigh 100 parts of epoxycyclohexyl propyl group cage-type silsesquioxane ((C9H15O)m(SiO1.5)8, wherein m=3), 0.8 part
Dark green, 0.8 part of diaryl group iodized salt, 2 parts of surfactants, storage stabilizing agent, the mixture of crosslinking agent and defoamer, with different
Propyl alcohol is solvent, and solvent quality is the 35% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, it is fully mixed
400nm is made after conjunction and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 8
Weigh 100 parts of epoxycyclohexyl propyl group cage-type silsesquioxane ((C9H15O)m(SiO1.5)8, wherein m=8), 3 parts of dimensions
Raw plain B2,3 parts of diaryl group iodized salts, 4 parts of surfactants, storage stabilizing agent, the mixture of adhesion promoter and defoamer,
Using propylene glycol methyl ether acetate as solvent, solvent quality is the 40% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in
440nm is made in propylene glycol methyl ether acetate, after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 9
Weigh 100 parts of epoxycyclohexyl propyl group cage-type silsesquioxane ((C9H15O)m(SiO1.5)8, wherein m=7), 5 parts of blood
Red pigment, 5 parts of triaryl salt compounded of iodine, the mixture of 5 parts of defoamers, crosslinking agent and adhesion promoter, with propylene glycol monomethyl ether acetic acid
Ester is solvent, and solvent quality is the 45% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in propylene glycol methyl ether acetate
In, 570nm is made after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 10
Weigh 100 parts of glycidol cage-type silsesquioxane ((C3H5O2)m(SiO1.5)8, wherein m=4), 1 part of methylene
The mixture of indigo plant, 1 part of isopropylbenzene cyclopentadienyl iron hexafluorophosphate, 2 parts of surfactants and defoamer, using acetone as solvent, solvent matter
Measure as the 50% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in acetone, 650nm is made after being sufficiently mixed and absorbs certainly
By base aggretion type two-photon resist.
Embodiment 11
Weigh 100 parts of glycidol cage-type silsesquioxane ((C3H5O2)m(SiO1.5)8, wherein m=6), 3.5 parts of rhodamines
B, 3.5 parts of diaryl group iodized salts, the mixture of 3 parts of surfactants, storage stabilizing agent and adhesion promoter, using isopropanol as
Solvent, solvent quality are the 55% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, made after being sufficiently mixed
Obtain 550nm and absorb radical polymerization mould assembly two-photon resist.
Embodiment 12
Weigh 100 parts of glycidol cage-type silsesquioxane ((C3H5O2)m(SiO1.5)8, wherein m=8), 5 surpass phthalein green grass or young crops, 5 parts
Isopropylbenzene cyclopentadienyl iron hexafluorophosphate, the mixture of 4 parts of surfactants, storage stabilizing agent and levelling agent are molten using ethanol as solvent
Agent quality is the 60% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in ethanol, 920nm is made after being sufficiently mixed and inhales
Receive radical polymerization mould assembly two-photon resist.
Embodiment 13
Weigh 100 parts of ethenyl cage model sesquialter siloxane ((C2H3)m(SiO1.5)8, wherein m=3), 2 parts of vitamin B2s, 2
The mixture of part benzoin ethyl ether, 1 part of surfactant and storage stabilizing agent, using acetone as solvent, solvent quality is above-mentioned each
The 65% of constituent mass summation.Above-mentioned each component is dissolved in acetone, 440nm is made after being sufficiently mixed and absorbs radical polymerization mould assembly
Two-photon resist.
Embodiment 14
Weigh 100 parts of ethenyl cage model sesquialter siloxane ((C2H3)m(SiO1.5)8, wherein m=6), 3.6 parts of dark greens,
3.6 parts of diphenylethans, 3.5 parts of defoamers, crosslinking agent, the mixture of adhesion promoter and levelling agent, using isopropanol to be molten
Agent, solvent quality are the 70% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, is made after being sufficiently mixed
660nm absorbs radical polymerization mould assembly two-photon resist.
Embodiment 15
Weigh 100 parts of ethenyl cage model sesquialter siloxane ((C2H3)m(SiO1.5)8, wherein m=7), 4.8 parts of ferrohemes,
4.8 parts of alpha-hydroxyalkyl benzophenones, 4.5 parts of surfactants, adhesion promoter, the mixture of levelling agent and defoamer, with the third two
Alcohol methyl ether acetate is solvent, and solvent quality is the 75% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in propane diols
570nm is made in methyl ether acetate, after being sufficiently mixed and absorbs radical polymerization mould assembly two-photon resist.
Embodiment 16
Weigh 100 parts of 3- mercaptopropyi cage-type silsesquioxanes ((C3H7S)m(SiO1.5)8, wherein m=2), 1.5 parts of Luo Dan
Bright B, 1.5 parts of α, alpha, alpha-dimethyl epoxide-α-phenyl acetophenone, the mixture of 2 parts of surfactants, storage stabilizing agent and crosslinking agent,
Using isopropanol as solvent, solvent quality is the 80% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, filled
550nm absorption radical polymerization mould assembly two-photon resists are made after dividing mixing.
Embodiment 17
Weigh 100 parts of 3- mercaptopropyi cage-type silsesquioxanes ((C3H7S)m(SiO1.5)8, wherein m=5), 3 parts of leaves are green
Element, 3 parts of bis(benzoylphenyl) phosphine oxides, the mixture of 3 parts of surfactants, adhesion promoter and defoamer, with acetone
For solvent, solvent quality is the 85% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in acetone, made after being sufficiently mixed
Obtain 456nm and absorb radical polymerization mould assembly two-photon resist.
Embodiment 18
Weigh 100 parts of 3- mercaptopropyi cage-type silsesquioxanes ((C3H7S)m(SiO1.5)8, wherein m=8), 5 parts of phthalein green grass or young crops
It is green, 5 parts of benzoin dimethylethers, 5 parts of crosslinking agents, adhesion promoter, the mixture of storage stabilizing agent and defoamer, with isopropanol
For solvent, solvent quality is the 95% of above-mentioned each component quality summation.Above-mentioned each component is dissolved in isopropanol, after being sufficiently mixed
660nm is made and absorbs radical polymerization mould assembly two-photon resist.
Two-photon resist performance test
1st, the resistance to elevated temperatures of two-photon resist
The two-photon resist 1mL prepared in Example 8, is uniformly coated on slide, is then placed on hot plate
110 DEG C are heated to 10 DEG C/min speed, after toasting 6h, room temperature is cooled to, is then transferred into 50mW.cm-2UVA solidification cases
In expose 20min, be then transferred on 95 DEG C of hot plate and heat 10min.Film after solidification is stripped down from slide, used
Thermogravimetic analysis (TGA) instrument establishes thermogravimetric curve of the resist in air and Ar gas shielded atmosphere, condition setting during test
For：Programming rate is 10 DEG C/min, and from room temperature to 550 DEG C, gained thermogravimetric curve is as shown in Fig. 2 as shown in Figure 2, be somebody's turn to do
Heat decomposition temperature of the resist in air and Ar gas is above 350 DEG C.
2nd, the spin coating performance of two-photon resist
(1) the two-photon resist prepared in Example 8 is used to configure Resist Solution, and each resist configured is molten
The mass fraction of resist is respectively 10%, 20%, 30%, 40%, 50%, 60% in liquid.
(2) silicon chip cuts into 1cm x 1cm fritter, the concentrated sulfuric acid/hydrogen peroxide (volume ratio 3 of the surface through boiling：1) clean
Take out after 5min, cleaned with substantial amounts of deionized water, dried.
(3) each Resist Solution forms the thickness of film under different whirl coating speed in testing procedure (1) respectively, specifically
Step is：Silicon chip after step of learning from else's experience (2) processing, is placed on 140 DEG C of hot plates and heats half an hour, removes surface-bonded water, so
Corresponding wafer center is added drop-wise to each Resist Solution 200uL in the quantitative aspiration step (1) of liquid-transfering gun afterwards, every kind of resist is molten
Liquid sets two parallel groups, and respectively with each spin coating 30s of 4000rpm and 7000rpm whirl coating speed, it is molten will then to coat resist
The silicon chip of liquid is placed in 50mW.cm-2UVA solidification cases in expose 30s, be then transferred on 95 DEG C of hot plate and heat 3min.With sharp
The film surface that is formed on each silicon chip of tweezers mark one of vestige, determine each film thickness, gained spin coating using step instrument
Curve can obtain as shown in figure 3, from the figure 3, it may be seen that by controlling the content of resist and whirl coating speed in Resist Solution
The controllable agent film against corrosion of 50nm-10um thickness, i.e. resist film thickness by control Resist Solution mass fraction and
Whirl coating speed determines.
3rd, the determination of composition after two-photon resist sinters
The two-photon resist prepared in Example 8, after exposed, the resist after 2g exposures is taken to be put into quartz boat
In, it is transferred in tube furnace.500 DEG C are risen to by room temperature under air and Ar atmosphere respectively, heating rate is 10 DEG C/min, and
1h is sintered at 500 DEG C, the sample after room temperature is cooled to and is understood through elementary analysis, organic moiety after being sintered in 500 DEG C of air atmospheres
Residue：C (3.1%), H (1.9%), O (13.5%), the residue of organic moiety after sintering in 500 DEG C of argon atmosphers：C
(16.1%), H (4.9%), O (2.8%)；Infrared spectrum analysis, as shown in Figure 4, it is known that characteristic peak 2800-300cm-1,
1450cm-1, 890cm-1Organic component through 500 DEG C sintering after disappear, it is 1020cm only to remain characteristic absorption-1With
780cm-1Oxidation silicon components；XPS constituent analyses, as shown in Figure 5, it is known that the carbon component of the resist is anxious after 500 DEG C of sintering
Reduce sharply few, Si, O valence state and SiO in product2It is very identical, the above analysis result, after finally determining resist sintering
Composition is class silicon dioxide structure CxSiOy。
4th, two-photon resist is exposed by UVA and obtains the mask plate graphic structure that resolution ratio is 2um
The two-photon resist prepared in Example 8 is used to configure Resist Solution, in the Resist Solution configured
The mass fraction of resist is 10%；Silicon chip cuts into 1cm × 1cm fritter, the concentrated sulfuric acid of the surface through boiling/hydrogen peroxide (body
Product ratio 3：1) take out after cleaning 5min, cleaned with substantial amounts of deionized water, dry, the silicon chip after drying is placed on 140 DEG C of heat
Heated on plate half an hour, remove surface-bonded water, Resist Solution 200uL is quantitatively then drawn with liquid-transfering gun and is added drop-wise in silicon chip
Centre, with 4000rpm whirl coating speed spin coating 30s, then by spin coating, the silicon chip of Resist Solution is placed in 60 DEG C of hot plate and gone forward
30min is dried, 95 DEG C is then warming up to, eliminates solvent.It is close on resist surface after covering the mask plate that resolution ratio is 2um, puts
In 50mW.cm-2UVA solidification cases in expose 30s, be then transferred on 95 DEG C of hot plate and heat 5min, after being cooled to room temperature, silicon
Piece is immersed in 10s in developer solution (using PGMEA as main component), takes out, is cleaned with plasma water, post bake on 60 DEG C of hot plate
1min, you can obtain the mask plate graphic structure that resolution ratio is 2um, as shown in Figure 6.
5th, two-photon resist is applied in two-photon photoetching
The two-photon resist prepared in Example 8 is used to configure Resist Solution, in the Resist Solution configured
The mass fraction of resist is 60%；Silicon chip cuts into 1cm × 1cm fritter, the concentrated sulfuric acid of the surface through boiling/hydrogen peroxide (body
Product ratio 3：1) take out after cleaning 5min, cleaned with substantial amounts of deionized water, dry, the silicon chip after drying is placed on 140 DEG C of heat
Heated on plate half an hour, remove surface-bonded water, Resist Solution 500uL is quantitatively then drawn with liquid-transfering gun and is added drop-wise in silicon chip
Centre, with 2000rpm whirl coating speed spin coating 30s, then by spin coating, the silicon chip of Resist Solution is placed in 60 DEG C of hot plate and gone forward
30min is dried, 95 DEG C is then warming up to, eliminates solvent, 10um thick resist films are made in silicon chip surface.Surface is covered with etching
The silicon chip of agent film is transferred on three-dimensional mobile piezoelectric movement platform.Adjust femtosecond pulse light path, output wavelength 400nm, work(
Rate is 5mW pulse laser, and laser is converged in piezoelectric movement platform by 100x object lens, focuses on laser spot spot diameter and is
300nm or so, and by focus spot position adjustments on the combination interface of etching agent film and silicon chip.XY directions are write in program
Cycle is 3um, and quantity 10, the Z-direction cycle is 1um, and the number of plies is 8 three-dimensional yard structure, passes through programme-control piezoelectric movement
The motion path of platform, movement velocity are the 200um/ seconds, complete the processing of three-dimensional yard structure.After process finishing, silicon chip is shifted
5min is heated on to 95 DEG C of hot plates, after being cooled to room temperature, silicon chip is immersed in developer solution (using PGMEA as main component) and surpassed
Raw cleaning 10s, takes out, with plasma water cleaning, drying, you can obtain three-dimensional yard structure, as shown in Figure 7.
With reference to the above method, by using the Resist Solution that 200uL mass fractions are 10%, with 3000pm whirl coating speed
Degree, 200nm thick resist films are prepared in silicon chip surface, utilize 400nm femtosecond pulses, progressive power 5mw-0.5mw, system
Into 50um × 50um network, the silicon chip with network is transferred in tube furnace, with 10 DEG C/minute in argon gas atmosphere
The speed of clock is warming up to 500 DEG C, and constant temperature is cooled to room temperature after 1 hour.Utilize grid before and after observation by light microscope high-temperature process
The change of structure, as shown in figure 8, it is complete to find that the network after 500 DEG C of processing preserves, further illustrate in the present invention
Resist has high-temperature stability.
6th, two-photon resist encloses grid nano-device for manufacture
The two-photon resist prepared in the present invention has nonlinear optical effect, is enclosed when using the manufacture of two-photon resist
During grid nano-device, energy source can reach shaded areas below silicon nanowires, so as to realize effective exposure of alternative gate structure,
And the resist in the present invention has excellent dielectricity, and heat endurance, be resistant to 350 DEG C of high temperature above, when carry out etc. from
During sub- CVD deposition, alternative gate structure is not damaged made of the resist, and when etched for grid structure, HF is molten
Liquid is deleted with selectivity to being substituted made of the resist.Two-photon resist is used to manufacture the technological process for enclosing grid nano-device
As shown in figure 9, it is specially：
The two-photon resist prepared in Example 8 is used to configure Resist Solution, in the Resist Solution configured
The mass fraction of resist is 40%；The silicon chip that hanging silicon nanowires is pre-machined is fixed on photoresist spinner, uses liquid-transfering gun
Quantitatively draw Resist Solution 300uL and be added drop-wise to wafer center, with 3000rpm whirl coating speed spin coating 30s, then by spin coating
The silicon chip of Resist Solution is placed in front baking 30min on 60 DEG C of hot plate, is then warming up to 95 DEG C, eliminates solvent, in silicon chip surface
1um thick resist films are made.The silicon chip that surface is covered with to etching agent film is transferred on three-dimensional mobile piezoelectric movement platform.Adjustment
Femtosecond pulse light path, output wavelength 400nm, power are 1mW pulse laser, and laser converges to silicon chip by 100x object lens
On hanging silicon nanowires near, it is 300nm or so to focus on laser spot spot diameter, and adjustment focus spot position adjustments are being carved
On the combination interface for losing agent film and silicon chip.It is 5um that length is write in program, and thickness is 1um lines, passes through programme-control pressure
The motion path of electric moveable platform, movement velocity are the 100um/ seconds, complete the processing of silicon nanowires alternative gate structure.Process finishing
Afterwards, silicon chip is transferred on 95 DEG C of hot plate and heats 5min, after being cooled to room temperature, silicon chip be immersed in developer solution (using PGMEA as
Main component) in excusing from death cleaning 5s, take out, with plasma water cleaning, drying, you can the alternative gate structure for obtaining silicon nanowires adds
Work.Then plasma CVD deposition Si is utilized3N4, x-ray irradiation alternative gate structure made of resist, make the alternative gate structure
It is changed into class silica structure, alternative gate structure is finally removed with HF selective etch, is backfilled with metallic gold, is finally prepared into three
Dimension encloses grid nano-device.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (9)
1. one kind is used for the resist of two-photon photoetching, it is characterised in that the resist includes component A and component B；By quality
Number meter, the component A include 100 parts of cage-type silsesquioxane compound, two-photon sensitising agent 0.1-5 parts, light trigger
0.1-5 parts, auxiliary agent 1-5 parts；The component B is the solvent of the 5-95% based on the component A gross masses；The cage model sesquialter silicon
The chemical formula of siloxane compound is Rm(SiO1.5)8, m is 2-8 positive integer, and R structure is as shown in any one of formula I-VI in formula：
N is positive integer in formula I-VI.
2. a kind of resist for being used for two-photon photoetching as claimed in claim 1, it is characterised in that the cage model sesquialter silica
When R structure is formula I or II in hydride compounds, the light trigger is in crack type photoinitiator or hydrogen-capture-type light initiator
One kind.
3. a kind of resist for being used for two-photon photoetching as claimed in claim 1, it is characterised in that the cage model sesquialter silica
When R structure is general formula III or IV in hydride compounds, the light trigger is cationic photoinitiator.
4. a kind of resist for being used for two-photon photoetching as claimed in claim 1, it is characterised in that the cage model sesquialter silica
When R structure is formula V or VI in hydride compounds, the light trigger is crack type photoinitiator.
5. one kind as described in claim any one of 1-4 is used for the resist of two-photon photoetching, it is characterised in that double light
Sub- sensitising agent is one kind in super phthalein green grass or young crops, dark green, ferroheme, chlorophyll, vitamin B2, methylene blue or rhodamine B.
6. one kind as described in claim any one of 1-4 is used for the resist of two-photon photoetching, it is characterised in that the auxiliary agent
For the one or more in surfactant, storage stabilizing agent, defoamer, crosslinking agent, adhesion promoter or levelling agent.
7. one kind as described in claim any one of 1-4 is used for the resist of two-photon photoetching, it is characterised in that the solvent
For one kind in propylene glycol methyl ether acetate, ethanol, isopropanol or acetone.
8. application of the resist in three-D micro-nano information apparatus are manufactured described in claim any one of 1-7.
9. application as claimed in claim 8, it is characterised in that the three-D micro-nano information apparatus are to enclose gate nano line device.
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| CN201710719138.0A CN107390471A (en) | 2017-08-21 | 2017-08-21 | One kind is used for resist and its application of two-photon photoetching |
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| CN113087913A (en) * | 2021-03-15 | 2021-07-09 | 北京化工大学常州先进材料研究院 | Double-bond modified cage-type silsesquioxane and photoresist composition thereof |
| CN113189844A (en) * | 2021-05-27 | 2021-07-30 | 广州一新科技有限公司 | Negative photoresist based on cage-shaped polysilsesquioxane and preparation method thereof |
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