CN106531613B - Selective modification processing method and device for graphene surface - Google Patents
Selective modification processing method and device for graphene surface Download PDFInfo
- Publication number
- CN106531613B CN106531613B CN201610258555.5A CN201610258555A CN106531613B CN 106531613 B CN106531613 B CN 106531613B CN 201610258555 A CN201610258555 A CN 201610258555A CN 106531613 B CN106531613 B CN 106531613B
- Authority
- CN
- China
- Prior art keywords
- laser
- substrate sample
- sample wafer
- graphene
- preset area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 230000004048 modification Effects 0.000 title claims description 20
- 238000012986 modification Methods 0.000 title claims description 20
- 238000003672 processing method Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 72
- 239000007789 gas Substances 0.000 claims description 20
- 239000010409 thin film Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000000427 thin-film deposition Methods 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 17
- 230000007547 defect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/0231—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to electromagnetic radiation, e.g. UV light
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66015—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene
- H01L29/66037—Multistep manufacturing processes of devices having a semiconductor body comprising semiconducting carbon, e.g. diamond, diamond-like carbon, graphene the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66045—Field-effect transistors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Electromagnetism (AREA)
- Carbon And Carbon Compounds (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a method and a device for modifying and processing a selected area of a graphene surface, wherein the method comprises the steps of scanning a preset area on the surface of a substrate sample by laser to improve the number of dangling bonds on the surface of a graphene film material covered by the preset area, and performing film deposition on the surface of the substrate sample by adopting an atomic layer deposition method to grow a target film in the preset area.
Description
Technical Field
The invention relates to the field of semiconductors, in particular to a graphene surface selective modification processing method and device.
Background
The continuous progress of functional thin film materials has promoted the rapid development of electronic information science. When the size of the functional material silicon of the traditional electronic information science is smaller than 10nm of line width, due to the influence of physical factors such as scale effect and the like, the breakthrough of the device performance is greatly restricted, and people are forced to explore new materials. Since the discovery of graphene, a monoatomic layer carbon material, which exists stably, by geom et al in 2004, research on two-dimensional thin-film materials represented by graphene has been progressing significantly.
Due to the specific optical, electrical, thermodynamic and mechanical properties of graphene, the graphene has many exciting properties and potential application prospects in the fields of microelectronics, quantum physics, materials, chemistry and the like. For example, graphene has room temperature electron mobility as high as 15,000cm2/(V-s), and in some forms even as high as 200,000cm 2/(V-s); the MoS2 bulk material is an indirect bandgap (0.65eV), the monoatomic layer MoS2 is a direct bandgap (1.79eV), and compared with a graphene material with a bandgap needing to be constructed, the graphene material can be more favorably applied to a field effect transistor.
The most typical method is to use graphene as a semiconductor material to prepare a high-performance field effect transistor, and along the development route of the microelectronic industry with the equal scaling reduction of the moore's law, the existing mature industrial production needs A L D (Atomic L a layer Deposition) to prepare an ultrathin high-k gate medium on the two-dimensional material graphene, however, the surface of the high-performance graphene film material does not usually have the necessary conditions of A L D film formation such as dangling bonds, and it is difficult to deposit a uniform high-retention high-k gate medium or other films on the surface of the graphene by adopting A L D Atomic layer by Atomic layer.
In the existing method, even if a surface modification method such as specific solution spin coating, plasma bombardment and the like is adopted to enable the surface of the graphene to have a dangling bond group suitable for film formation, in a subsequent patterning process for preparing a gate dielectric structure, great difficulty still exists because a two-dimensional thin layer material is prepared uniformly without damage. In the existing subsequent processes, patterning preparation schemes such as plasma etching thinning and organic material transfer adhesion are adopted, but in the schemes, the control of etching rate, the introduction of functional groups into the base surface of the two-dimensional material, the control of key parameters such as irregular etching pits caused on the surface of the two-dimensional material, anisotropic etching ratio and the like still have great problems, very serious defects are introduced into the prepared two-dimensional materials such as graphene and the like, and the application of the two-dimensional materials in the aspect of devices is limited.
That is to say, the graphene film material surface in the prior art usually does not have the essential conditions for forming a film of a L D such as dangling bonds, and the like, and has the technical problem that it is difficult to grow a film by atomic layer deposition of a L D.
Disclosure of Invention
The invention provides a method and a device for processing the selective modification of the surface of graphene, and solves the technical problems that the surface of a graphene film material in the prior art usually does not have the essential conditions of A L D film formation such as dangling bonds and the like, and the film is difficult to grow by adopting A L D atomic layer-by-atomic layer deposition.
On one hand, in order to solve the technical problems, the invention provides the following technical scheme:
a graphene surface selective modification processing method comprises the following steps:
scanning a preset area on the surface of a substrate sample wafer by using laser so as to increase the number of dangling bonds on the surface of the graphene film material covered by the preset area;
and performing film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target film in the preset area.
Optionally, before scanning the preset region on the surface of the substrate sample with the laser, the method further includes: and setting the wavelength, power and scanning path of the laser.
Optionally, the wavelength of the laser is 150nm to 1500 nm.
Optionally, the laser is a pulse laser; the single pulse width of the laser is 10-8s～10-12s。
Optionally, the laser is focused by a lens group; the diameter of the laser focusing spot is 0.1-5 mm.
Optionally, the number of atomic layers of the graphene film material is 1-50.
Optionally, the target film is a high-k gate dielectric; the high-k gate dielectric is specifically made of the following materials: al (Al)2O3、ZrO2、HfO2、HfSiOx、SiO2、TiN、La2O3、LaAlOxOr Hf L aOx。
Optionally, before scanning the preset area on the surface of the substrate sample by using the laser, the method further comprises the step of drawing vacuum so that the vacuum degree of the substrate sample is 1 × 105～1×10-9Pa in vacuum environment.
Optionally, before scanning the preset region on the surface of the substrate sample with the laser, the method further includes: inputting gas to enable the substrate sample wafer to be in the gas atmosphere; the gas is specifically any one or mixture of more of the following gases: oxygen, hydrogen, nitrogen, helium, and argon.
In another aspect, a graphene surface selective modification processing device is provided, the device including:
the laser scanning device comprises a laser scanning cavity, wherein a slide glass platform is arranged in the laser scanning cavity; an optical window flange component and a sample introduction channel for taking and placing a substrate sample wafer are arranged on the laser scanning cavity;
the device comprises a laser light source and a lens group array, wherein laser emitted by the laser light source is focused by the lens group array, and then a preset area on the surface of a substrate sample placed on a slide glass platform is scanned through an optical window flange component, so that the number of dangling bonds on the surface of a graphene film material covered by the preset area is increased;
the atomic layer deposition equipment cavity is communicated with the laser scanning cavity through a sample wafer transmission pipeline; and after the substrate sample wafer subjected to laser scanning enters the atomic layer deposition equipment cavity through the sample wafer transmission pipeline, performing thin film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target thin film in the preset area.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. according to the method and the device provided by the embodiment of the application, the designed graph structure is formed by laser scanning, a large number of dangling bonds or defects are introduced into the surface of the graphene film material within the scanning range, so that the adhesive force of the surface of the graphene film material within the preset graph structure range to an atomic layer is increased, the preparation of the selected area film by adopting an atomic layer deposition method is facilitated, and films such as uniform and high-shape-preserving high-k gate dielectrics and the like are grown.
2. According to the method and the device provided by the embodiment of the application, the target film material to be prepared is uniformly spread on the graphene film in situ, so that the problems of multiple transfer, defects caused by the intermediate layer material, environmental pollution and the like can be avoided. Meanwhile, the method is compatible with a large-scale manufacturing process of a silicon-based device, so that the manufacturing and research of a high-performance two-dimensional thin-film material device can continue to use a large-scale plane printing process, the process flow is simple and controllable, the repeatability is good, and the method can be used for automatic mass production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is apparent that the drawings in the following description are only embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a flowchart of a processing method for selective modification of graphene surface in an embodiment of the present application;
fig. 2 is a structural diagram of a graphene surface selective modification processing device in an embodiment of the present application.
Detailed Description
The embodiment of the application provides a graphene surface area selection modification processing method and device, and solves the technical problems that in the prior art, the surface of a graphene film material does not usually have essential conditions for A L D film formation such as a dangling bond and the like, and the film is difficult to grow by adopting A L D atomic layer-by-atomic layer deposition.
In order to solve the above technical problem, the general idea of the technical solution provided in the embodiments of the present application is as follows:
the application provides a graphene surface area selection modification processing method, which comprises the following steps:
scanning a preset area on the surface of a substrate sample wafer by using laser so as to increase the number of dangling bonds on the surface of the graphene film material covered by the preset area;
and performing film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target film in the preset area.
According to the method and the device provided by the embodiment of the application, the designed graph structure is formed by laser scanning, a large number of dangling bonds or defects are introduced into the surface of the graphene film material within the scanning range, so that the adhesive force of the surface of the graphene film material within the preset graph structure range to an atomic layer is increased, the preparation of the selected area film by adopting an atomic layer deposition method is facilitated, and films such as uniform and high-shape-preserving high-k gate dielectrics and the like are grown.
In order to better understand the technical solutions, the technical solutions will be described in detail below with reference to specific embodiments, and it should be understood that the specific features in the examples and the embodiments of the present invention are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the examples and the embodiments of the present application may be combined with each other without conflict.
Example one
In this embodiment, a method for modifying and processing a selected region of a graphene surface is provided, please refer to fig. 1, fig. 1 is a flowchart of the method for modifying and processing the selected region of the graphene surface in the embodiment of the present application, as shown in fig. 1, the method includes:
step S101, scanning a preset area on the surface of a substrate sample wafer by using laser to increase the number of dangling bonds on the surface of a graphene film material covered by the preset area;
and S102, performing thin film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target thin film in the preset area.
In the embodiment of the application, the target thin film can be a high-k gate dielectric; the high-k gate dielectric is specifically made of the following materials: al (Al)2O3、ZrO2、HfO2、HfSiOx、SiO2、TiN、La2O3、LaAlOxOr Hf L aOx。
Of course, the target film may also be a film grown by using a L D, such as a copper wiring layer, a metal gate dielectric, and the like, which is not limited in this embodiment.
The principle and the specific implementation steps of the method provided by the embodiment are described in detail as follows:
first, the principle of the method provided by the present embodiment is described:
because A L D is a film deposited by a self-limiting reaction mechanism of a chemical source on the surface of the substrate, and the surface layer of the two-dimensional atomic crystal graphene has no dangling bond, the film cannot be formed by chemical adsorption of the precursor on the graphene to realize nucleation growth, namely the film cannot be formed.
The dynamic characteristics of scanning laser energy, irradiance and other light pulse absorption processes are finely regulated, lattice adsorption butt joint in the continuous oscillation process of graphene polar molecules is induced, laser can also induce decomposition and chemical adsorption of hybridized carbon atoms on the surface of graphene in a specific atmosphere environment, and a large number of dangling bonds or defects are introduced to the surface of a graphene two-dimensional film material in a scanning range, for example, partial C-C bonds in surface layer lattices of the film are broken to form C-O, C-N and other groups with affinity energy, so that nucleation growth and selective area film preparation are facilitated by adopting an atomic layer deposition method.
Next, the specific implementation steps of the method provided by this embodiment are described:
before step S101 is executed, film formation preparation may be performed, which specifically includes:
preparing a sample: a substrate sample wafer with a surface covered with a two-dimensional graphene film material is placed on a slide glass platform, and the slide glass platform is adjusted to a processing positioning point.
In the embodiment of the application, the number of atomic layers of the graphene film material is 1-50.
Preferably, the covalent bond functionalized energy density threshold of the graphene film material is 0.1mJ/cm2～100J/cm2。
In the embodiment of the present application, the slide platform is a platform capable of moving along the directions X, Y and Z perpendicular to each other, so as to adjust the substrate sample to a processing positioning point, and to position a processing range in a selected area.
Laser setting: and setting processing parameters such as wavelength, power and scanning path of the laser.
Specifically, the selected processing parameters are set as an optimal damage threshold required for the functionalization of the surface covalent bonds of the graphene film material monoatomic layer.
Preferably, the wavelength of the laser can be set to be 150nm in extreme ultraviolet to 1500nm in near infrared.
Preferably, the laser may be set to be a pulsed laser; the single pulse width of the laser is 10-8s～10-12s。
Preferably, the laser scanning speed range is 1 mm/s-10000 mm/s.
Preferably, the laser is focused by a lens group; the diameter of the laser focusing spot is 0.1-5 mm.
Setting an environment: in the embodiment of the present application, the processing method for modifying the surface of the graphene thin film material by using the selective area of the graphene surface can be performed in an environment such as vacuum, atmosphere, or reaction gas atmosphere, which is not limited herein.
Preferably, before scanning the preset area on the surface of the substrate sample by the laser, the method further comprises the step of drawing vacuum so that the vacuum degree of the substrate sample is 1 × 105～1×10-9Pa in vacuum environment.
Specifically, the total system and the detection module can be started, and the vacuum of different levels can be adjusted until the vacuum degree of each system reaches the working pressure range.
Preferably, before scanning the predetermined region on the surface of the substrate sample with the laser, the method further includes: inputting gas to enable the substrate sample wafer to be in the gas atmosphere, so that a large number of dangling bonds or defects are introduced to the surface of the graphene two-dimensional thin film material in the scanning range, for example, partial C-C bonds in crystal lattices on the surface layer of the thin film are broken to form groups with affinity energy such as C-O, C-N, C-OH; the gas is specifically any one or mixture of more of the following gases: oxygen, hydrogen, nitrogen, helium, and argon.
After the preparation of film formation, step S101 is executed, a preset area on the surface of the substrate sample is scanned by laser, so as to increase the number of dangling bonds on the surface of the graphene film material covered by the preset area.
Specifically, taking the target film as a gate medium as an example, focusing laser on the surface of a graphene film material on a substrate, and then performing selective scanning modification on the preset area of the substrate surface by using the laser with set parameters; in this embodiment of the application, the preset region is a preset pattern structure of the gate dielectric, that is, a region where the gate dielectric needs to be grown.
And then, performing step S102 on the substrate sample wafer after the laser scanning is completed in step S101, that is, performing film deposition on the surface of the substrate sample wafer by using an atomic layer deposition method to grow a target film in the preset region until the gate structure film growth is completed in the preset region, so as to form a designed gate dielectric or other film patterns.
Specifically, the designed graph structure is scanned by laser, on one hand, a large number of dangling bonds or defects are introduced into the surface of the graphene film material within the scanning range, so that the adhesion of the surface of the graphene film material within the preset graph structure range to an atomic layer is increased, the preparation of the selective area film by adopting an atomic layer deposition method is facilitated, and uniform and high-shape-preserving films such as high-k gate dielectrics and the like are grown. On the other hand, the prepared material can be uniformly spread on the film in situ, and the problems of multiple transfer, defects caused by intermediate layer materials, environmental pollution and the like can be avoided. Meanwhile, the method is compatible with a large-scale manufacturing process of a silicon-based device, so that the manufacturing and research of a high-performance two-dimensional thin-film material device can continue to use a large-scale plane printing process, the process flow is simple and controllable, the repeatability is good, and the method can be used for automatic mass production.
Based on the same inventive concept, the application also provides a device for executing the method in the first embodiment, which is detailed in the second embodiment.
Example two
In this embodiment, a graphene surface selective modification processing apparatus is provided, please refer to fig. 2, fig. 2 is a structural diagram of the graphene surface selective modification processing apparatus in the embodiment of the present application, as shown in fig. 2, the apparatus includes:
the device comprises a laser scanning cavity 1, wherein a slide glass platform 2 for placing a substrate sample is arranged in the laser scanning cavity 1; an optical window flange component 3 and a sample introduction channel 5 for taking and placing a substrate sample wafer 4 are arranged on the laser scanning cavity 1;
the device comprises a laser light source 6 and a lens group array 7, wherein laser emitted by the laser light source 6 is focused by the lens group array 7, and then a preset area on the surface of a substrate sample 4 placed on a slide glass platform 2 is scanned through an optical window flange component 3, so that the number of dangling bonds on the surface of a graphene film material covered by the preset area is increased;
the atomic layer deposition equipment cavity 8 is communicated with the laser scanning cavity 1 through a sample wafer transmission pipeline 9;
after the substrate sample 4 is scanned by the laser in the laser scanning cavity 1, the substrate sample enters the atomic layer deposition equipment cavity 8 through the sample conveying pipeline 9, and in the atomic layer deposition equipment cavity 8, the atomic layer deposition method is adopted to perform thin film deposition on the surface of the substrate sample 4 so as to grow a target thin film in the preset area.
Preferably, the slide platform 2 can hold and hold various types of substrate coupons having dimensions in the range of <18 inch side lengths.
Preferably, the optical window flange component 3 is a flange component in a specific wavelength range of 50nm to 2000 nm.
Preferably, the transportation pipeline 9 can be set to 1Pa to 5 × 10-8And (4) a vacuum environment of Pa, and transferring samples in the vacuum environment to ensure that the affinity groups on the surface of the graphene scanned by the laser in the step S101 are not damaged, so that the nucleation growth by adopting an atomic layer deposition method is facilitated.
Preferably, a valve 10 may be further disposed in the transportation pipeline 9 to avoid mutual atmosphere influence of the laser scanning cavity 1 and the atomic layer deposition equipment cavity 8.
In the embodiment of the present application, as shown in fig. 2, the apparatus may further include: a computer data acquisition, processing and control system 11, wherein the system 11 is connected with the laser light source 6 and is used for setting processing parameters such as wavelength, power and scanning path of the laser light source 6;
the apparatus may further include: the gas path 12 is arranged on the laser scanning cavity 1 and used for inputting gas so as to enable the substrate sample wafer to be in the gas atmosphere;
the apparatus may further include: the vacuum gauge assembly 13 is arranged on the laser scanning cavity 1, and is used for vacuumizing the laser scanning cavity 1 according to a preset vacuum condition;
the apparatus may further include: the main cavity pump set 14 is arranged on the laser scanning cavity 1, and is used for providing power for modules arranged on the laser scanning cavity 1.
The working method and principle of the device in the embodiment have been described in detail in the first embodiment, and for the sake of brevity of the description, the description will not be repeated here.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
1. according to the method and the device provided by the embodiment of the application, the designed graph structure is formed by laser scanning, a large number of dangling bonds or defects are introduced into the surface of the graphene film material within the scanning range, so that the adhesive force of the surface of the graphene film material within the preset graph structure range to an atomic layer is increased, the preparation of the selected area film by adopting an atomic layer deposition method is facilitated, and films such as uniform and high-shape-preserving high-k gate dielectrics and the like are grown.
2. According to the method and the device provided by the embodiment of the application, the target film material to be prepared is uniformly spread on the graphene film in situ, so that the problems of multiple transfer, defects caused by the intermediate layer material, environmental pollution and the like can be avoided. Meanwhile, the method is compatible with a large-scale manufacturing process of a silicon-based device, so that the manufacturing and research of a high-performance two-dimensional thin-film material device can continue to use a large-scale plane printing process, the process flow is simple and controllable, the repeatability is good, and the method can be used for automatic mass production.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (2)
1. A graphene surface selective modification processing method is characterized by comprising the following steps:
scanning a preset area on the surface of a substrate sample wafer by using laser so as to increase the number of dangling bonds on the surface of the graphene film material covered by the preset area;
performing film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target film in the preset area;
wherein, before scanning the preset area on the surface of the substrate sample wafer with the laser, the method further comprises:
setting the wavelength, power and scanning path of the laser;
the wavelength of the laser is from extreme ultraviolet 150nm to near infrared 1500 nm;
the laser is pulse laser; the single pulse width of the laser is 10-8s～10-12s；
The laser is focused through a lens group; the diameter of the laser focusing spot is 0.1 mu m-5 mm;
the number of atomic layers of the graphene film material is 1-50;
the target film is a high-k gate dielectric; the high-k gate dielectric is specifically made of the following materials: al (Al)2O3、ZrO2、HfO2、HfSiOx、SiO2、TiN、La2O3、LaAlOxOr Hf L aOx；
Before scanning the preset area on the surface of the substrate sample wafer by using the laser, the method further comprises the following steps:
vacuum is drawn to make the substrate sample wafer have a vacuum degree of 1 × 105～1×10-9Pa vacuum environment;
before scanning the preset area on the surface of the substrate sample wafer by using the laser, the method further comprises the following steps:
inputting gas to enable the substrate sample wafer to be in the gas atmosphere; the gas is specifically any one or mixture of more of the following gases:
oxygen, hydrogen, nitrogen, helium, and argon.
2. A graphene surface selective modification processing device is characterized by comprising:
the laser scanning device comprises a laser scanning cavity, wherein a slide glass platform is arranged in the laser scanning cavity; an optical window flange component and a sample introduction channel for taking and placing a substrate sample wafer are arranged on the laser scanning cavity;
the device comprises a laser light source and a lens group array, wherein laser emitted by the laser light source is focused by the lens group array, and then a preset area on the surface of a substrate sample placed on a slide glass platform is scanned through an optical window flange component, so that the number of dangling bonds on the surface of a graphene film material covered by the preset area is increased;
the atomic layer deposition equipment cavity is communicated with the laser scanning cavity through a sample wafer transmission pipeline; after the substrate sample wafer subjected to laser scanning enters the atomic layer deposition equipment cavity through the sample wafer transmission pipeline, performing thin film deposition on the surface of the substrate sample wafer by adopting an atomic layer deposition method so as to grow a target thin film in the preset area;
the apparatus may further include: the gas circuit is arranged on the laser scanning cavity and used for inputting gas so that the substrate sample wafer is in the gas atmosphere, and the gas is specifically the mixture of any one or more of the following gases: oxygen, hydrogen, nitrogen, helium, and argon;
the apparatus may further compriseA vacuum gauge component arranged on the laser scanning cavity and used for vacuumizing the laser scanning cavity so as to ensure that the substrate sample wafer is in a vacuum degree of 1 × 105～1×10-9Pa in vacuum environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610258555.5A CN106531613B (en) | 2016-04-22 | 2016-04-22 | Selective modification processing method and device for graphene surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610258555.5A CN106531613B (en) | 2016-04-22 | 2016-04-22 | Selective modification processing method and device for graphene surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106531613A CN106531613A (en) | 2017-03-22 |
| CN106531613B true CN106531613B (en) | 2020-07-17 |
Family
ID=58358130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610258555.5A Active CN106531613B (en) | 2016-04-22 | 2016-04-22 | Selective modification processing method and device for graphene surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106531613B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492502B (en) * | 2017-07-26 | 2020-08-21 | 山东理工大学 | Method for treating graphene surface by using benzene series steam and application |
| CN110550624A (en) * | 2018-05-31 | 2019-12-10 | 中国科学院微电子研究所 | Processing method of graphene film material |
| CN110548996A (en) * | 2018-06-01 | 2019-12-10 | 中国科学院微电子研究所 | method and device for selecting and etching graphene |
| CN109598322B (en) * | 2018-11-08 | 2021-08-27 | 首都师范大学 | Method for encrypting, reading and writing information by using nanotechnology |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097297A (en) * | 2010-11-16 | 2011-06-15 | 复旦大学 | Method for depositing high k gate dielectrics on atomic layer on graphene surface by adopting electric field induction |
| CN102709177A (en) * | 2012-06-14 | 2012-10-03 | 复旦大学 | Method for growing high k dielectric on graphene by adopting rhodamine as buffering layer |
| CN102856184A (en) * | 2012-10-11 | 2013-01-02 | 中国科学院上海微系统与信息技术研究所 | Method for preparing high-k gate medium on surface of multi-layer graphene |
| CN103903961A (en) * | 2014-04-11 | 2014-07-02 | 北京大学 | Method for depositing high k gate medium on graphene material and application |
| CN103915327A (en) * | 2014-03-05 | 2014-07-09 | 复旦大学 | Method for using insular graphene pieces to grow high-K media on graphene |
| CN103915348A (en) * | 2014-04-19 | 2014-07-09 | 复旦大学 | Method for manufacturing graphene nanowire device |
| CN104851791A (en) * | 2015-04-29 | 2015-08-19 | 西交利物浦大学 | Method for depositing high-K gate dielectric on atomic layer on surface of graphene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010122635A1 (en) * | 2009-04-21 | 2010-10-28 | 富士通株式会社 | Method for processing graphene sheet material and method for manufacturing electronic device |
| US8614435B2 (en) * | 2009-11-03 | 2013-12-24 | International Business Machines Corporation | Utilization of organic buffer layer to fabricate high performance carbon nanoelectronic devices |
| US10266963B2 (en) * | 2013-03-08 | 2019-04-23 | The United States Of America, As Represented By The Secretary Of The Navy | Growth of crystalline materials on two-dimensional inert materials |
| CN103318878B (en) * | 2013-06-27 | 2016-04-06 | 江南石墨烯研究院 | A kind of oversized shape is than the preparation method and its usage of graphene microchip |
| KR102099440B1 (en) * | 2013-10-11 | 2020-05-15 | 엘지이노텍 주식회사 | A method of manufacturing a light emitting device |
-
2016
- 2016-04-22 CN CN201610258555.5A patent/CN106531613B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097297A (en) * | 2010-11-16 | 2011-06-15 | 复旦大学 | Method for depositing high k gate dielectrics on atomic layer on graphene surface by adopting electric field induction |
| CN102709177A (en) * | 2012-06-14 | 2012-10-03 | 复旦大学 | Method for growing high k dielectric on graphene by adopting rhodamine as buffering layer |
| CN102856184A (en) * | 2012-10-11 | 2013-01-02 | 中国科学院上海微系统与信息技术研究所 | Method for preparing high-k gate medium on surface of multi-layer graphene |
| CN103915327A (en) * | 2014-03-05 | 2014-07-09 | 复旦大学 | Method for using insular graphene pieces to grow high-K media on graphene |
| CN103903961A (en) * | 2014-04-11 | 2014-07-02 | 北京大学 | Method for depositing high k gate medium on graphene material and application |
| CN103915348A (en) * | 2014-04-19 | 2014-07-09 | 复旦大学 | Method for manufacturing graphene nanowire device |
| CN104851791A (en) * | 2015-04-29 | 2015-08-19 | 西交利物浦大学 | Method for depositing high-K gate dielectric on atomic layer on surface of graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106531613A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106531613B (en) | Selective modification processing method and device for graphene surface | |
| US9941380B2 (en) | Graphene transistor and related methods | |
| US8431103B2 (en) | Method of manufacturing graphene, graphene manufactured by the method, conductive film comprising the graphene, transparent electrode comprising the graphene, and radiating or heating device comprising the graphene | |
| JP6359484B2 (en) | Method for providing lateral heat treatment of a thin film on a low temperature substrate | |
| Li et al. | Atomic layer deposition of Al2O3 directly on 2D materials for high‐performance electronics | |
| JP2020533808A (en) | Defect removal of selective deposition by chemical etching | |
| JP6124300B2 (en) | Method for producing graphene laminate and method for producing transparent electrode using the graphene laminate | |
| Ye et al. | Doping of semiconductors by molecular monolayers: monolayer formation, dopant diffusion and applications | |
| JP2007186413A5 (en) | ||
| US9741568B2 (en) | Sulfur doping method for graphene | |
| CN107217242B (en) | Surface modification method for dielectric substrate of electronic device | |
| CN113206005A (en) | Laser manufacturing method for two-dimensional material tensile strain engineering | |
| Zhang et al. | Wafer‐Scale Fabrication of Suspended Single‐Walled Carbon Nanotube Arrays by Silver Liquid Dynamics | |
| Tian et al. | Production of large‐area nucleus‐free single‐crystal graphene‐mesh metamaterials with zigzag edges | |
| US20190256998A1 (en) | Location-specific growth and transfer of single crystalline tmd monolayer arrays | |
| Yuan et al. | Stacking transfer of wafer-scale graphene-based van der Waals superlattices | |
| KR101741313B1 (en) | Doping method of graphene based on a supporting layer with ion implantation | |
| Choi et al. | Unusually high optical transparency in hexagonal nanopatterned graphene with enhanced conductivity by chemical doping | |
| US20220177313A1 (en) | Graphene nanoribbon composite structure and method for making the same | |
| JP2005288636A (en) | Carbon nano-tube forming method using nano-indent edge and anti-dot catalyst array | |
| CN113206006A (en) | Laser impact preparation method for two-dimensional material tensile strain engineering | |
| CN113066905A (en) | Method for preparing indium selenide photoelectric detector by photoetching technology | |
| Okinaka et al. | Direct nanoimprint of inorganic-organic hybrid glass | |
| Jung et al. | Polymer material as a gate dielectric for graphene field-effect-transistor applications | |
| CN110607517B (en) | Method for cleaning graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |