CN107217242A - A kind of surface modification method of electronic device dielectric substrate - Google Patents
A kind of surface modification method of electronic device dielectric substrate Download PDFInfo
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- CN107217242A CN107217242A CN201710360173.8A CN201710360173A CN107217242A CN 107217242 A CN107217242 A CN 107217242A CN 201710360173 A CN201710360173 A CN 201710360173A CN 107217242 A CN107217242 A CN 107217242A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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Abstract
The invention belongs to technical field of electronic devices, specially a kind of surface modification method of electronic device dielectric substrate.The present invention is the hexagonal boron nitride film in dielectric substrate surface direct growth two-dimensional structure, and thickness is between 1 100nm, the modification for interface between electronic device semiconductor and dielectric layer.The present invention reaches growth and the quasi-equilibrium of etching during plasma gas phase deposition by controlling material concentration, so as to realize that the hexagonal boron nitride film of two-dimensional structure grows in the on-catalytic of dielectric surface.The inventive method is simple, cost is low, does not need shifting process, whole process compatible with semiconductor technology to operate at low temperature in.The present invention can also three-dimensional surface syntype modification on hexagonal boron nitride film, and can large area prepare.The present invention can improve carrier in electronic device semiconductor and the mobility of dielectric interface, while the thermal contact resistance of semiconductor and dielectric interface can be reduced, improve thermal conductive property and device stability.
Description
Technical field
The invention belongs to technical field of electronic devices, and in particular to the surface modification method of electronic device dielectric substrate.
Background technology
In in the past few decades, fast development and the need of raising equipment computing capability with modern electronic technology
Ask, improving carrier mobility and reduction interface resistance becomes extremely important.Electric charge transfer occurs in dielectric in electronic device
Between layer and semiconductor material layer, while can also produce Joule heat at the interface.Therefore, medium interface is improving device mobility
And heat dissipating properties are very important.But up to the present also few methods by modifying medium interface are while take into account
To raising mobility and heat dissipating properties.
Hexagonal boron nitride film is a species grapheme material, and nitrogen-atoms and boron atom pass through sp2Hydridization constitutes 6 side's points
The cellular two-dimensional structure of battle array.It is a kind of broad-band gap insulator, with good mechanical strength, electrical insulating property, thermal conductivity, chemistry
Stability.Therefore, boron nitride is widely used in terms of as protective layer and dielectric layer.At present, no catalyst chemical gas
Phase sedimentation grows hexagonal boron nitride film, it is necessary to which higher growth temperature height causes the high cost of high energy consumption.Plasma chemistry
Although vapour deposition can grow hexagonal boron nitride at low temperature, particulate amorphous, unordered shape or three is presented in product
Tie up the hexagonal boron nitride of structure.At present, the two-dimensional structure hexagonal boron nitride film of on-catalytic growing large-area is still at low temperature
It is highly difficult.In addition, although had many work that hexagonal boron nitride is applied into dielectric surface at present and improved electronic device migration
Rate, but it is not applied to the precedent that heat dissipating properties energy is improved at semiconductor/dielectric substrate interface also.
The content of the invention
In view of the shortcomings of the prior art, present invention offer is a kind of can improve the electronics of the stability of device at high power
The surface modification method of device dielectric substrate.
We have found that in plasma chemical vapor deposition growth course, control precursor concentration can realize six side's nitrogen
Change the reversible balance of boron growth and etching, so as to grow high-quality two-dimentional six side under the conditions of the quasi-equilibrium of the reversible reaction
Boron nitride pellicle.The Plasma-Modified technology that the present invention is provided is except thin in the two-dimentional hexagonal boron nitride of dielectric substrate surface modification
Beyond film, additionally it is possible to syntype in the two-dimentional hexagonal boron nitride film of dielectric substrate surface modification with three-dimensional structure.The present invention
The carrier mobility of electronic device can be improved, while the thermal contact resistance of semiconductor and dielectric interface can be reduced, so that
Improve the stability of device at high power.
The surface modification method for the electronic device dielectric substrate that the present invention is provided, is comprised the following steps that：
The first step, clean dielectric substrate is placed in the reaction cavity of plasma chemical vapor deposition system；System is led to
Enter carrier gas and control air pressure in 1mTorr ~ 100Torr scopes, be heated to 200 ~ 800 DEG C, be slowly introducing precursors；
Second step, plasma is applied in the growth district of material, and power is 0.1~1000 watt, and the duration is 1~200
Minute；It is preferred that power is 1~500 watt, the duration is 20~100 minutes；
3rd step, stops heating, naturally cools to room temperature, dielectric substrate surface obtains the hexagonal boron nitride film of two-dimensional structure.
The dielectric substrate of hexagonal boron nitride film has been modified, can be directly used for preparing electronic device.
Wherein, the thickness of the hexagonal boron nitride film of two-dimensional structure is between 1-100nm, and preferred thickness is 20-100nm.
Wherein, gaseous mixture of the described carrier gas selected from hydrogen, argon gas, nitrogen, oxygen, helium, air, and above-mentioned gas
Body.
Wherein, described dielectric substrate is the silicon substrate with oxide layer, mica, quartz, silicon nitride, hafnium oxide, three
Al 2 O and the above-mentioned dielectric substrate with three-dimensional structure.
Wherein, the presoma of described plasma method growth hexagonal boron nitride film is N2, BNH6, NH3, BH3,
B3N3H6, BNH4, BH2BH2Deng the molecule with boron element and nitrogen.
Wherein, described precursors are passed through mode and are：Gaseous precursor is passed through reaction cavity by gas flowmeter；
Solid precursor is placed through the mode that slowly distils of heating and is passed through reaction cavity；Liquid precursor be placed through heating volatilization or
The mode that carrier gas is brought into is passed through reaction cavity.
Wherein, described plasma method modification substrate surface needs accurate control precursor concentration, and scope is per minute
0.0001-10mol boron nitrogen source is passed through, growth and the quasi-equilibrium of etching during plasma gas phase deposition is reached, realizes two
Tie up on-catalytic large area deposition of the hexagonal boron nitride film in dielectric surface of structure.
Wherein, described electronic device includes field-effect transistor, light emitting diode, photoelectric sensor, chemical sensor
Deng the electricity component with dielectric layer and semiconductor material interface.Described semi-conducting material is transition metal dichalcogenide, stone
The two-dimensional materials such as black alkene, the inorganic semiconductor material such as silicon, germanium, selenium, gallium nitride, GaAs, gallium phosphide, indium phosphide, and simultaneously five
The organic semiconducting materials such as benzene, metal phthalocyanine, metalloporphyrin, polythiophene.
Being a little relative to existing method of the invention：（1）Simple technical method is easy to operate, and cost is low, can realize
Large area is modified；（2）Two-dimentional hexagonal boron nitride film can be modified in the dielectric surface with three-dimensional structure syntype；（3）Should
Technology can improve the thermal contact resistance of the carrier mobility of electronic device, reduction semiconductor and dielectric interface.
Brief description of the drawings
Fig. 1 is the Raman of the two-dimentional hexagonal boron nitride film of growth in embodiment 1（Raman）Spectrum and x-ray photoelectron
Power spectrum.Wherein, left figure is the Raman spectrum of hexagonal boron nitride, and middle figure is the x-ray photoelectron power spectrum of boron atom, and right figure is that nitrogen is former
The x-ray photoelectron power spectrum of son.
Fig. 2 is the atomic force of tungsten selenide material in embodiment 1（AFM）Collection of illustrative plates, wherein,（a）For shape appearance figure,（b）To draw
It is graceful（Raman）Spectrum,（c）For fluorescence（PL）Spectrum.
Fig. 3 is heretofore described field-effect transistor schematic diagram.
Fig. 4 is two tungsten selenide field-effect transistors of the substrate preparation of the two-dimentional hexagonal boron nitride film of modification in embodiment 1
Transfer characteristic curve, and two tungsten selenide field-effect transistors prepared by the substrate without the two-dimentional hexagonal boron nitride film of modification
Transfer characteristic curve.
Fig. 5 is the median surface thermo-resistance measurement related data of embodiment 1.
Fig. 6 is the median surface thermo-resistance measurement related data of embodiment 2.
Fig. 7 is the SiO with three-dimensional structure in embodiment 32Scanning after/Si substrate growths two dimension hexagonal boron nitride film
Electron microscope image and x-ray photoelectron power spectrum.Wherein,（a）For a kind of D S iO2/ Si substrate SEM
Figure,（b）For the x-ray photoelectron power spectrum of boron atom in the hexagonal boron nitride of a Growns,（c）For the six of a Growns
The x-ray photoelectron power spectrum of nitrogen-atoms in square boron nitride,（d）For another D S iO2/ Si substrate scanning electron microscope diagrams,
（e）For the x-ray photoelectron power spectrum of boron atom in the hexagonal boron nitride of d Growns,（f）For six sides of d Growns
The x-ray photoelectron power spectrum of nitrogen-atoms in boron nitride.
Label in figure：1 gold electrode；2 tungsten selenides；3 hexagonal boron nitride films；4 insulating barriers；5 grids.
Embodiment
The present invention is further described below by specific embodiment.
Embodiment 1：
The first step, prepares one piece of 1cm × 1cm p-type heavy doping silicon chip, there is silica after one layer of 300nm on surface first.With different
Propyl alcohol and deionized water ultrasound（100 watts are cleaned 60 minutes）Clean up.Then clean silicon chip is placed on plasma chemistry
In gas-phase deposition system；
Second step, 10 are evacuated down to by plasma chemical vapor deposition system-3Torr, then will be passed through stabilization in device
Argon gas and hydrogen are than the air-flow for the sccm of 100 sccm/10, then begin to warm up；
3rd step, plasma chemical vapor deposition system is heated to 500 DEG C, while by BNH6Presoma is slowly heated to 110
DEG C distillation；
4th step, plasma intensity is applied in the growth district of material, and power level is 30 watts, and the duration is 30 points
Clock；
5th step, closes heating power supply, naturally cools to room temperature, two-dimentional six sides nitrogen is obtained in the silicon chip surface with silica
Change boron membrane（Fig. 1）；
6th step, the substrate for modifying two-dimentional hexagonal boron nitride is placed in chemical gas-phase deposition system and grows two-dimentional two tungsten selenide
Material（Fig. 3）；
7th step, directly prepares field-effect transistor specific configuration step as follows with material made from the 6th step：（1）Use electronics
Beam exposes and hot evaporation method prepares electrode pair in two-dimentional tungsten selenide, and the electrode pair is gold electrode, with two-dimentional tungsten selenide material
Material connection, thickness is 30nm.Field-effect transistor structure is as shown in Figure 3.（2）Measure the electrical properties of field-effect transistor.Adopt
The field-effect transistor mobility for modifying substrate with hexagonal boron nitride is 77 cm2V-1S-1, hence it is evident that higher than in no hexagonal boron nitride
Modify the field-effect transistor of substrate, the cm of mobility 1.42V-1S-1.Fig. 4 is transfer characteristic curve.(3) field effect transistor is measured
The heat dispersion of pipe.Test data is as shown in Figure 5.After being modified using hexagonal boron nitride, the interface of two tungsten selenides and dielectric substrate
Thermal resistance reduces (4.55 ± 0.25) × 10-8 m2KW-1。
Embodiment 2：
According to the method in embodiment 1, its difference is：6th step, the substrate for modifying two-dimentional hexagonal boron nitride is placed
Two-dimentional two selenizings Mo is grown in chemical gas-phase deposition system.7th step, measures the heat dispersion of field-effect transistor.Survey
Try data as shown in Figure 6.After being modified using hexagonal boron nitride, the interface resistance of two selenizing molybdenums and dielectric substrate reduces (1.21
±0.20) ×10-7 m2KW-1。
Embodiment 3：
According to the method for the first step in embodiment 1 to the 5th step, difference is：Use the SiO with three-dimensional structure2/Si
Substrate.After being modified by plasma chemical vapor deposition, the scanning electron microscope image and hexagonal boron nitride of substrate
The x-ray photoelectron power spectrum of film is as shown in Figure 7.
Claims (8)
1. a kind of surface modification method of electronic device dielectric substrate, it is characterised in that comprise the following steps that：
The first step, dielectric substrate is placed in the reaction cavity of plasma chemical vapor deposition system；System is passed through carrier gas
And control air pressure in 1mTorr ~ 100Torr scopes, 200 ~ 800 DEG C are heated to, before the reaction for being passed through growth hexagonal boron nitride film
Drive body；
Second step, plasma is applied in the growth district of material, and power is 0.1~1000 watt, and the duration is 1~200
Minute；
3rd step, stops heating, naturally cools to room temperature, dielectric substrate surface obtains the hexagonal boron nitride film of two-dimensional structure；
4th step, is directly used in electronic device by the dielectric substrate for being modified with hexagonal boron nitride film and prepares.
2. the surface modification method of electronic device dielectric substrate according to claim 1, it is characterised in that described carrier gas
Mixed gas selected from hydrogen, argon gas, nitrogen, oxygen, helium, air, and above-mentioned gas.
3. the surface modification method of electronic device dielectric substrate according to claim 1, it is characterised in that described dielectric
Substrate is the silicon substrate with oxide layer, mica, quartz, silicon nitride, hafnium oxide, alundum (Al2O3), or with three-dimensional knot
The above-mentioned dielectric substrate of structure.
4. the surface modification method of the electronic device dielectric substrate according to claim 1,2 or 3, it is characterised in that described
The precursors for growing hexagonal boron nitride film are N2、BNH6 、NH3、 BH3、 B3N3H6、 BNH4Or BH2BH2。
5. the surface modification method of electronic device dielectric substrate according to claim 4, it is characterised in that described reaction
Presoma is passed through mode：Gaseous precursor is passed through reaction cavity by gas flowmeter；Solid precursor is placed through heating
The mode slowly distilled is passed through reaction cavity；Liquid precursor is placed through the mode that heating is volatilized or carrier gas is brought into and is passed through reaction
Cavity.
6. the surface modification method of electronic device dielectric substrate according to claim 5, it is characterised in that control presoma
Concentration is passed through 0.0001-10mol to be per minute, reaches growth and the quasi-equilibrium of etching during plasma gas phase deposition, with
Realize on-catalytic large area deposition of the hexagonal boron nitride film in dielectric surface of two-dimensional structure.
7. the surface modification method of the electronic device dielectric substrate according to claim 1,2,3,5 or 6, it is characterised in that
The thickness of the hexagonal boron nitride film of two-dimensional structure is between 1-100nm.
8. the surface modification method of electronic device dielectric substrate according to claim 7, it is characterised in that described electronics
Device is the electricity component with dielectric layer and semiconductor material interface；Described semi-conducting material is selected from transition metal curing
Thing, grapheme two-dimension material, silicon, germanium, selenium, gallium nitride, GaAs, gallium phosphide, indium phosphide inorganic semiconductor material, and simultaneously five
Benzene, metal phthalocyanine, metalloporphyrin, polythiophene organic semiconducting materials.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108447914A (en) * | 2018-02-05 | 2018-08-24 | 华东师范大学 | One kind being based on VO2Flexible thin-film transistor and its application |
| CN108461484A (en) * | 2018-04-09 | 2018-08-28 | 黄山学院 | A kind of encapsulating structure and processing technology of high reliability IGBT module |
| CN109518278A (en) * | 2018-11-12 | 2019-03-26 | 厦门大学 | A kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping |
| CN111068051A (en) * | 2018-10-19 | 2020-04-28 | 华东师范大学 | Diagnosis and treatment integrated nanoprobe based on copper phthalocyanine molecule and preparation and application thereof |
| US20220165568A1 (en) * | 2019-03-15 | 2022-05-26 | Tokyo Electron Limited | Method and device for forming hexagonal boron nitride film |
| CN117550621A (en) * | 2024-01-11 | 2024-02-13 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
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| CN108447914A (en) * | 2018-02-05 | 2018-08-24 | 华东师范大学 | One kind being based on VO2Flexible thin-film transistor and its application |
| CN108461484A (en) * | 2018-04-09 | 2018-08-28 | 黄山学院 | A kind of encapsulating structure and processing technology of high reliability IGBT module |
| CN108461484B (en) * | 2018-04-09 | 2023-09-15 | 黄山学院 | Packaging structure and processing technology of IGBT module |
| CN111068051A (en) * | 2018-10-19 | 2020-04-28 | 华东师范大学 | Diagnosis and treatment integrated nanoprobe based on copper phthalocyanine molecule and preparation and application thereof |
| CN111068051B (en) * | 2018-10-19 | 2022-06-21 | 华东师范大学 | Diagnosis and treatment integrated nanoprobe based on copper phthalocyanine molecule and preparation and application thereof |
| CN109518278A (en) * | 2018-11-12 | 2019-03-26 | 厦门大学 | A kind of method of richness nitrogen atmosphere enhancing boron nitride pellicle p-type electric-conducting doping |
| CN109518278B (en) * | 2018-11-12 | 2020-12-08 | 厦门大学 | Method for enhancing p-type conductive doping of boron nitride film by nitrogen-rich atmosphere |
| US20220165568A1 (en) * | 2019-03-15 | 2022-05-26 | Tokyo Electron Limited | Method and device for forming hexagonal boron nitride film |
| CN117550621A (en) * | 2024-01-11 | 2024-02-13 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
| CN117550621B (en) * | 2024-01-11 | 2024-03-22 | 恒泰军航高分子材料(山东)有限公司 | Method and device for preparing high-purity BN ceramic precursor |
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