CN103456604B - Substrate processing method for improving mobility of carbon-based semiconductor device - Google Patents
Substrate processing method for improving mobility of carbon-based semiconductor device Download PDFInfo
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- CN103456604B CN103456604B CN201310414069.4A CN201310414069A CN103456604B CN 103456604 B CN103456604 B CN 103456604B CN 201310414069 A CN201310414069 A CN 201310414069A CN 103456604 B CN103456604 B CN 103456604B
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- 239000000758 substrate Substances 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title abstract description 21
- 239000004065 semiconductor Substances 0.000 title abstract description 9
- 238000003672 processing method Methods 0.000 title abstract 2
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- 230000005669 field effect Effects 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 44
- 229910000077 silane Inorganic materials 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- -1 methoxyl group Chemical group 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000002411 adverse Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention discloses a substrate processing method for improving mobility of a carbon-based semiconductor device, which utilizes a silane coupling agent organic film layer to passivate and modify the surface of the carbon-based semiconductor device. According to the invention, the substrate with the surface treated by the silane coupling agent is used, so that adverse effects on the graphene field effect device caused by polarity scattering and impurity adsorption of the surface of the substrate are reduced, the carrier mobility of the device is effectively increased, and the performance of the device is improved.
Description
Technical field
The present invention relates to the semiconductor device fabrication processes based on material with carbon element, particularly a kind of carbon that improvesThe Method of processing a substrate of based semiconductor device mobility, belongs to nano-electron technical field.
Background technology
Nanoelectronics taking material with carbon element as base, especially with CNT (CarbonNanotube)And Graphene (Graphene) nanoelectronics that is base, be considered to have great application prospect,Be rich in the alternative silica-base material of potentiality. Since CNT in 1991 and Graphene in 2004 are by successSince development, carbon back electronics has been obtained great development. Electronics based on carbon back have size little,The features such as speed is fast, low in energy consumption, technique is simple, are subject to people and pay close attention to more and more widely.
For carbon back semiconductor devices, because conductive carbon material only has one or several atomic layers thickDegree, so it has an important feature, conductive carbon material, to the surface being in contact with it, comprises liningBasal surface and dielectric surface, very responsive; Substrate surface situation can significantly affect the surface state of material with carbon element,In material with carbon element, introduce new scattering mechanism, cause remarkable decline and the device of material with carbon element carrier mobilityPart performance degradation.
Use silane coupler organic film to process former substrate, passivation, modification substrate surface, subtractLittle of the carbon that substrate surface polar scattering, the fluctuating of surperficial hollow, impurity absorption etc. are former thereby causeThe decline of sill hydraulic performance decline, especially carrier mobility. And by adjusting silane couplerThe parameter such as concentration proportioning, sedimentation time, can effectively adjust thickness and the table of silane organic filmSurface roughness. Silane coupler is easy to dehydrating condensation simultaneously, can firmly be attached to polytypeSubstrate surface, and have stronger tolerance. This novel, simple, Method of processing a substrate willDevelopment to carbon back electronic device plays an important role.
Summary of the invention
(1) technical problem that will solve
The object of the present invention is to provide a kind of substrate processing that improves carbon back semiconductor devices mobilityMethod, is with to graphene field effect device due to substrate surface polar scattering and impurity absorption reducingThe harmful effect coming, increases device carrier mobility, improves device performance.
(2) technical scheme
For achieving the above object, the invention provides a kind of lining that improves carbon back semiconductor devices mobilityTreatment of bottom, the method is to utilize silane coupler organic film to come passivation and modified carbon base semiconductorDevice substrate surface, specifically comprises the following steps:
Step 1: the substrate after cleaning is put into 120 DEG C of dry processing 20 minutes of baking oven;
Step 2: preparation silane coupler solution, utilize organic solvent dissolution diluted silane coupling agent,Will process substrate immerses in dilution;
Step 3: under nitrogen or air ambient, the substrate after infiltrating is heated to 100 DEG C～150 DEG C,Make silane coupler monomer generate condensate in substrate surface generation dehydration condensation, thereby at substrateSurface forms silane coupler organic film.
In such scheme, described in step 2, dissolve the also organic solvent of diluted silane coupling agent, to siliconAlkane coupling agent has diluting effect, and does not react; The proportioning of described silane coupler and its dilutionFor 1:400-1:50 (volume ratio), the time that substrate immerses in dilution is 1-10 minute. Described moltenSeparate and the organic solvent of diluted silane coupling agent comprises: toluene, dimethylbenzene, ethyl acetate, acetone,The mixed solution of butanone, various alcohols or alcohol and water.
In such scheme, the silane coupler described in step 2 is single silane coupler, orThe mixture that two or more contain difference in functionality group silane coupling agent. Described silane coupler bagDraw together the methoxy or ethoxy silane that contains several functions group. Described several functions group be amino,Vinyl, phenyl, epoxy radicals, fluorine-based, chloro or nitro.
In such scheme, described in step 3, the temperature of heating is lower, needs the time of heating just longer,The temperature of heating is higher, needs the time of heating just shorter. Heating-up temperature is greater than or equal to 100 DEG CAnd while being less than 150 DEG C, keeping after 20 minutes～40 minutes at this heating-up temperature place constant temperature, then natureBe cooled to normal temperature.
In such scheme, after the dehydrating condensation of silane coupler described in step 3, form at substrate surfaceSilane coupler organic film is monolayer, and thickness is 3nm.
In such scheme, described in step 3, to the condensation of silane coupler thermal dehydration, adopt hot plate to addHeat, baking oven heating or diamond heating, heating-up temperature is at 100-150 degree Celsius, the dehydrating condensation timeAt 10-40 minute.
In such scheme, described in step 3 after substrate surface forms silane coupler organic film,Also comprise: again graphene film or CNT are transferred to substrate surface.
(3) beneficial effect
The Method of processing a substrate of this raising carbon back semiconductor devices mobility provided by the invention, due toUse the substrate of processing surface through silane coupler, so reduced because substrate surface polarity is loosePenetrate the harmful effect bringing to graphene field effect device with impurity absorption, effectively increased device and carriedStream transport factor, has improved device performance, for the realization of carbon back high performance device provides a solutionScheme, has met the demand of carbon back scale integrated circuit. Particularly, use silane coupler pairSubstrate carries out surface treatment, and its main advantage is embodied in:
1, be to carry out passivation, modify substrate surface with silane coupler organic film, can reduce due to liningFormer thereby the carbon-based material performance that causes such as basal surface polar scattering, the fluctuating of surperficial hollow, impurity absorptionDecline, the especially decline of carrier mobility
2, it is controlled that silane coupler has organic film thickness, by adjust coupling agent matched proportion density andSubstrate infiltrates sedimentation time, can realize the regulation and control to thicknesses of layers and surface roughness.
3, after silane coupler dehydrating condensation, form at substrate surface the monolayer that is about 3nm thicknessOrganic film, can firmly be attached to the multiple inorganic matters such as silicon, silica, metal, metal oxideSubstrate surface, technique is simple, reproducible.
Brief description of the drawings
Fig. 1 is that silane coupler reacts schematic diagram with inorganic matter substrate.
Fig. 2 is that the present invention uses silane coupler to carry out surface-treated flow chart to former substrate.
Fig. 3 shifts special according to the back of the body grid of the graphene field effect transistor device of the embodiment of the present invention 1Property (Ids-Vg) curve.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with concrete realityExecute example, and with reference to accompanying drawing, the present invention is described in more detail.
It is organic that Fig. 1 is that silane coupler monomer and inorganic matter substrate form monolayer by dehydrating condensationThe reaction mechanism schematic diagram of film. First described silane coupler is hydrolyzed, and dehydrating condensation becomes many thenAggressiveness, then with the hydroxy generation hydration of inorganic matter substrate surface, finally make it de-by heat dryingWater, finally forms silane coupler unimolecule rete at substrate surface.
Embodiment 1: use CVD growing graphene material, in two of process silane coupler processingOn silica/silicon substrate, realize graphene field effect transistor.
Fig. 2 is that the embodiment of the present invention is used silane coupler to carry out surface-treated flow chart to substrate,Comprise the following steps:
Step 1: the 100nm silica/silicon substrate after cleaning is put into 120 DEG C of dry places of baking ovenManage 20 minutes;
Step 2: configuration silane coupler-n-pro-pyl trimethoxy silane dilution, by n-pro-pyl threeMethoxy silane (purchased from Chinese Medicine group chemical reagent Beijing Co., Ltd) and ethanol solutionWith volume ratio, 1:100 dilutes, and fully shakes up after dilution, and substrate is immersed to 5 points of silane dilutionsClock;
Step 3: substrate is put into baking oven, logical N in casing2Protect, baking oven is warmed up to100 degrees Celsius, keep 30 minutes, temperature is reduced to normal temperature, take out substrate, measure n-pro-pyl front threeTMOS organic film thickness is 3nm;
Step 4: CVD growing graphene film transfer is arrived through n-pro-pyl trimethoxy silane placeOn silica/silicon substrate after reason;
Step 5: form figure by beamwriter lithography on grapheme material, electron beam evaporation one deckTitanium/gold (Ti/Au=10/50nm) metal that 10nm/50nm is thick, then puts into acetone by sample and peels off,Remove unwanted metal level, obtain needed electrode, thereby realize back of the body grid shape and grid shape field, topEffect tube device.
Fig. 3 shifts special according to the back of the body grid of the graphene field effect transistor device of the embodiment of the present invention 1Property (Ids-Vg) curve. Using n-pro-pyl trimethoxy silane to carry out, after surface treatment, subtracting to substrateLittle of substrate surface polar scattering and impurity absorption are brought not to graphene field effect deviceGood impact. Actual measured results shows, device effective mobility on average from using less than 2000cm2/ Vs rises to and exceedes 4000cm2/Vs。
Embodiment 2: use micromechanics to peel off grapheme material, at process n-pro-pyl trimethoxy silaneOn the silica/silicon substrate of processing, realize graphene field effect transistor.
Concrete steps are similar to Example 1, but the graphene film of in step 4, micromechanics being peeled off turnsMove on to through on aminopropyl trimethoxysilane silica/silicon substrate after treatment, and then realize stoneChina ink alkene FET device.
Embodiment 3: use CVD growing graphene material, in process aminopropyl trimethoxysilaneOn the silica/silicon substrate of processing, realize graphene field effect transistor.
Concrete steps are similar to Example 1, but in step 2, use aminopropyl trimethoxysilane to substituteN-pro-pyl trimethoxy silane and isopropyl alcohol dilute with volume ratio 1:100, and substrate infiltrates depositionTime is 10 minutes. After step 3, measuring aminopropyl trimethoxysilane organic film thickness is 5nm.
Same, through test, carbon-based field-effect transistors prepared by above-mentioned 3 embodiment is owing to makingWith the substrate of processing surface through silane coupler, reduce due to substrate surface polar scattering and assortedMatter is adsorbed the harmful effect bringing to graphene field effect device, has effectively increased device carrier and has movedMove rate, improved device performance.
Above-described specific embodiment, carries out object of the present invention, technical scheme and beneficial effectFurther description, institute it should be understood that the foregoing is only specific embodiments of the invention and, be not limited to the present invention, within the spirit and principles in the present invention all, any repairing of doingProtection scope of the present invention changes, be equal to replacement, improvement etc., within all should be included in.
Claims (9)
1. improve a Method of processing a substrate for graphene field effect transistor mobility, its feature existsIn, the method is to utilize silane coupler organic film to come passivation and grapheme modified field-effect transistorSubstrate surface, specifically comprises the following steps:
Step 1: the substrate after cleaning is put into 120 DEG C of dry processing 20 minutes of baking oven;
Step 2: preparation silane coupler solution, utilize organic solvent dissolution diluted silane coupling agent,Will process substrate immerses in dilution;
Step 3: under nitrogen or air ambient, the substrate after infiltrating is heated to 100 DEG C～150 DEG C,Make silane coupler monomer generate condensate in substrate surface generation dehydration condensation, thereby at substrateSurface forms silane coupler organic film;
Wherein, the silane forming at substrate surface after the dehydrating condensation of silane coupler described in step 3 is evenConnection agent organic film is monolayer, and thickness is 3nm; Described in step 3, the substrate after infiltrating is addedHeat, to 100 DEG C～150 DEG C, makes silane coupler monomer generate in substrate surface generation dehydration condensationCondensate, adopts hot plate heating, baking oven heating or diamond heating, and heating-up temperature is taken the photograph at 100-150Family name's degree, the dehydrating condensation time is at 10-40 minute.
2. the substrate place of raising graphene field effect transistor mobility according to claim 1Reason method, is characterized in that, dissolves the also organic solvent of diluted silane coupling agent described in step 2,Silane coupler is had to diluting effect, and do not react; Described silane coupler and its dilutionProportioning is volume ratio 1:400-1:50, and the time that substrate immerses in dilution is 1-10 minute.
3. the substrate place of raising graphene field effect transistor mobility according to claim 2Reason method, is characterized in that, the organic solvent of described dissolving diluted silane coupling agent comprises: toluene,The mixed solution of dimethylbenzene, ethyl acetate, acetone, butanone, various alcohols or alcohol and water.
4. the substrate place of raising graphene field effect transistor mobility according to claim 1Reason method, is characterized in that, the silane coupler described in step 2 is single silane coupler, orPerson is the multiple mixture that contains difference in functionality group silane coupling agent.
5. the substrate place of raising graphene field effect transistor mobility according to claim 4Reason method, is characterized in that, described silane coupler comprises the methoxyl group that contains several functions groupOr Ethoxysilane.
6. the substrate place of raising graphene field effect transistor mobility according to claim 5Reason method, is characterized in that, described several functions group is amino, vinyl, phenyl, epoxyBase, fluorine-based, chloro or nitro.
7. the substrate place of raising graphene field effect transistor mobility according to claim 1Reason method, is characterized in that, described in step 3, the temperature of heating is lower, just needs the time of heatingLonger, the temperature of heating is higher, needs the time of heating just shorter.
8. the substrate place of raising graphene field effect transistor mobility according to claim 7Reason method, is characterized in that, heating-up temperature is greater than or equal to 100 DEG C and while being less than 150 DEG C,This heating-up temperature place constant temperature keeps after 20 minutes～40 minutes, then naturally cools to normal temperature.
9. the substrate place of raising graphene field effect transistor mobility according to claim 1Reason method, is characterized in that, described in step 3, forms silane coupler organic film at substrate surfaceAfterwards, also comprise: again graphene film is transferred to substrate surface.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403498B1 (en) * | 1997-03-28 | 2002-06-11 | Tokyo Electron Limited | Method and device for treating substrate |
| CN101425565A (en) * | 2007-09-28 | 2009-05-06 | 大日本印刷株式会社 | Electroluminescent cell and manufacture method thereof |
| CN102593169A (en) * | 2011-01-07 | 2012-07-18 | 中国科学院微电子研究所 | Carbon-based field effect transistor and preparation method thereof |
| CN102627409A (en) * | 2011-12-14 | 2012-08-08 | 京东方科技集团股份有限公司 | Method for preparing carbon nanotube film |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403498B1 (en) * | 1997-03-28 | 2002-06-11 | Tokyo Electron Limited | Method and device for treating substrate |
| CN101425565A (en) * | 2007-09-28 | 2009-05-06 | 大日本印刷株式会社 | Electroluminescent cell and manufacture method thereof |
| CN102593169A (en) * | 2011-01-07 | 2012-07-18 | 中国科学院微电子研究所 | Carbon-based field effect transistor and preparation method thereof |
| CN102627409A (en) * | 2011-12-14 | 2012-08-08 | 京东方科技集团股份有限公司 | Method for preparing carbon nanotube film |
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