CN108516541A - A kind of novel C VD graphenes dry method transfer method - Google Patents
A kind of novel C VD graphenes dry method transfer method Download PDFInfo
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- CN108516541A CN108516541A CN201810320411.7A CN201810320411A CN108516541A CN 108516541 A CN108516541 A CN 108516541A CN 201810320411 A CN201810320411 A CN 201810320411A CN 108516541 A CN108516541 A CN 108516541A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The invention discloses a kind of novel C VD graphenes dry method transfer methods, and the PVP glue and PVA glue of spin coating configuration, baking oven are dried successively on graphene/copper foil；The PVA/PVP/ graphenes of gained/copper foil is taken out, remove PVA/PVP/ graphene films, then the film of stripping is transferred among the transparent glass slide of two panels, preheating, after so that film is unfolded naturally, immerses in the absolute ethyl alcohol of warm and is taken out after 5s, it is adhered on the substrate after cleaning, it waits for being placed in 10min in 75 DEG C of vapor after natural drying, is placed in baking oven drying；PVA/PVP/ graphenes/substrate is taken out, is placed in 75 DEG C of deionized water, after removing PVA/PVP colloids, deionized water is cleaned 5 times, baking oven drying.The present invention has protection glue residua less, heavy metal free residual, and organic solvent residual is few, the transfer graphene used time is few, at low cost, shifts the advantages that black alkene quality is higher.
Description
Technical field
The present invention relates to chemical fields, and in particular to a kind of novel C VD graphenes dry method transfer method.
Background technology
Graphene has high conductivity, the two-dimensional material of high heat conductance in the industries such as lithium battery and solar energy as a kind of
It has also been employed that, graphene is dissociateed using graphite from University of Manchester professor in 2004, Nobel Laureate's lid nurse et al.
Since 14 years between, the research about graphene is like a raging fire, the preparation of graphene, electric property, optical property, mechanicalness
It can, be modified and application aspect has been obtained for widely accepting.With the development of electronics field of photoelectric devices, graphene conduct
The two-dimensional material of a kind of high conductivity and the high transmittance to full spectrum is applied on the photoelectric device and is used as transparent electricity
Pole greatly improves the photoelectric respone rate of device.The preparation method of graphene has very much, mainly has：Utilize pyrolytic graphite
Graphene is separated；Carbon in silicon carbide is precipitated by high temperature；Using the method for chemical vapor deposition directly in substrate
Upper growth etc..Wherein, use is exactly directly grown using chemical vapor deposition on substrate most extensively, using most ripe, this
The graphene monocrystalline that method is grown is superior in quality, can meet the application on device, and this method has been obtained for promoting and realize
Volume production.But this method growth graphene is limited by substrate, high-purity copper foil is commonly used as substrate, it is clear by high temperature
After washing, it is passed through raw-gas and is grown.So the graphene film prepared is applied in device, shifting process is not
It can or lack.Traditional transfer method is the transfer of graphene wet method, and first even PMMA (polymethyl methacrylate) glue, reuses quarter
Erosion agent (such as ferric trichloride, ammonium persulfate) etches away copper foil, once purged that graphene is transferred to substrate surface again, finally goes
Glue.Graphene quality after this method transfer is preferable, and structure is more complete, and fold is less.But the technics comparing is complicated, etching
The copper substrate time is long, and prolonged etching has large effect to the adhesiveness of graphene film and PMMA glue, to
Graphene integrality during etching copper foil is caused to be affected.In addition, this method has the shortcomings that its is inherent：1, a huge sum of money
Belong to residual (such as Fe of impurity3+、Cu2+Deng)；2, the residual of PMMA colloids；3, the use of a large amount of organic solvents (such as acetone).
Invention content
To solve the above problems, being remained the present invention provides a kind of heavy metal free residual, without colloid, the stone that organic contamination is few
Black alkene dry method transfer method；The method is for using graphene as being very for transparent electrode and heterojunction photoelectric device
It is advantageous.
To achieve the above object, the technical solution that the present invention takes is：
A kind of novel C VD graphenes dry method transfer method, includes the following steps：
S1, PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol) colloid are prepared；
PVP glue：1g PVP white powders are weighed, 1ml deionized waters are added, then 2ml NVP (n- vinyl is added thereto
Pyrrolones), absolute ethyl alcohol is eventually adding to 10ml, and hand operated mixing, to being completely dissolved, sealing, (0 DEG C -4 DEG C) of low temperature are protected
It deposits；
PVA glue：1g PVA white powders are weighed, 10ml deionized waters are added, are placed on magnetic stirring apparatus, temperature setting is
80 DEG C, mixing time 1h, be in sticky glue until being completely dissolved, sealing, room temperature preserve；
S2, in order spin coating colloid；
Graphene/copper foil of size needed for clip, puts it into closed deionized water, uses 50 DEG C of heating water bath 3h
Afterwards, it takes out, the PVP glue and PVA glue obtained by spin coating successively in its graphene face, baking oven drying；
S3, the PVA/PVP/ graphenes of gained/copper foil is taken out, removes PVA/PVP/ graphene films, it then will stripping
Film be transferred among the transparent glass slide of two panels, on hot plate 75 DEG C preheating 90s, so that film is unfolded naturally；
S4, transfer graphene
Naturally the PVA/PVP/ graphene films unfolded are immersed in 50 DEG C of absolute ethyl alcohol and is taken out after 5s, be adhered to cleaning
Later it on substrate, waits for being placed in 10min in 75 DEG C of vapor after natural drying, film and substrate secure adhesion, are placed at this time
Baking oven is dried, and 110 DEG C, time 10min of oven temperature obtains PVA/PVP/ graphenes/substrate；
S5, it removes photoresist
PVA/PVP/ graphenes/substrate is taken out, 10min-15min in 75 DEG C of deionized water is placed in, removes PVA/PVP
It after colloid, is placed in deionized water and cleans 5 times, be placed in baking oven drying, you can, it is preferable that the temperature of baking oven is 110 DEG C, processing
Time be 10min.
Preferably, the step S2 specifically comprises the following steps：
Graphene/copper foil of size needed for S21, clip, puts it into closed deionized water, is added using 50 DEG C of water-baths
It after hot 3h, takes out, the PVP glue in its graphene face as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：Low speed 1000
Rev/min time 6s, 2000 revs/min of time 30s of high speed, spin coating 2 times transfer them to hot plate drying, heat after spin coating
75 DEG C of plate temperature, time 90s；
S22, by the PVA glue on the PVP glue after drying as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：Low speed
1000 revs/min of time 6s, 4000 revs/min of time 30s of high speed, spin coating 1 time transfer them to baking oven baking after spin coating
It is dry, 110 DEG C of oven temperature, time 15min.
The invention has the advantages that：
Less with protection glue residua, heavy metal free residual, organic solvent residual is few, the transfer graphene used time is few, cost
It is low, the advantages that black alkene quality is higher is shifted, the transfer of more traditional wet method more has foreground, the preparation to graphene and application industry
For have good facilitation and larger attraction.
Description of the drawings
Fig. 1 is the process flow chart of the embodiment of the present invention.
Specific implementation mode
In order to make objects and advantages of the present invention be more clearly understood, the present invention is carried out with reference to embodiments further
It is described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
As shown in Figure 1, an embodiment of the present invention provides a kind of novel C VD graphenes dry method transfer methods, including walk as follows
Suddenly：
S1, PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol) colloid are prepared；
PVP glue：1g PVP white powders are weighed, 1ml deionized waters are added, then 2ml NVP (n- vinyl is added thereto
Pyrrolones), absolute ethyl alcohol is eventually adding to 10ml, and hand operated mixing, to being completely dissolved, sealing, (0 DEG C -4 DEG C) of low temperature are protected
It deposits；
PVA glue：1g PVA white powders are weighed, 10ml deionized waters are added, are placed on magnetic stirring apparatus, temperature setting is
80 DEG C, mixing time 1h, be in sticky glue until being completely dissolved, sealing, room temperature preserve；
S2, in order spin coating colloid；
Graphene/copper foil of size needed for S21, clip, puts it into closed deionized water, is added using 50 DEG C of water-baths
It after hot 3h, takes out, the PVP glue in its graphene face as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：Low speed 1000
Rev/min time 6s, 2000 revs/min of time 30s of high speed, spin coating 2 times transfer them to hot plate drying, heat after spin coating
75 DEG C of plate temperature, time 90s；
S22, by the PVA glue on the PVP glue after drying as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：Low speed
1000 revs/min of time 6s, 4000 revs/min of time 30s of high speed, spin coating 1 time transfer them to baking oven baking after spin coating
It is dry, 110 DEG C of oven temperature, time 15min.
S3, the PVA/PVP/ graphenes of gained/copper foil is taken out, removes PVA/PVP/ graphene films, it then will stripping
Film be transferred among the transparent glass slide of two panels, on hot plate 75 DEG C preheating 90s, so that film is unfolded naturally；
S4, transfer graphene
Naturally the PVA/PVP/ graphene films unfolded are immersed in 50 DEG C of absolute ethyl alcohol and is taken out after 5s, be adhered to cleaning
Later it on substrate, waits for being placed in 10min in 75 DEG C of vapor after natural drying, film and substrate secure adhesion, are placed at this time
Baking oven is dried, and 110 DEG C, time 10min of oven temperature obtains PVA/PVP/ graphenes/substrate；
S5, it removes photoresist
PVA/PVP/ graphenes/substrate is taken out, 10min-15min in 75 DEG C of deionized water is placed in, removes PVA/PVP
It after colloid, is placed in deionized water and cleans 5 times, be placed in baking oven drying, you can.
The hydrosol is applied in the transfer of CVD graphenes by this specific implementation for the first time, and this method and traditional wet method shift work
It the features such as skill compares, and possesses simple for process, heavy metal free impurity residual, and colloid residual is few, and organic contamination is few, is shifted using dry method
Method transfer graphene can prepare phototube preferably close to its intrinsic performance in electricity, mechanics, optics etc.
There is greatly value in terms of part, energy storage material.On the one hand, which uses water-soluble Protection glue, in the mistake of transfer
Its chemical property can be kept stable in journey, and will not with graphene occur it is any react, during removing photoresist, utilize 75 DEG C of perseverances
The deionized water of temperature can preferably remove this layer of Protection glue, and after removing photoresist, the colloid residual on sample is less, will not be to graphene
The performance of device has an impact；On the other hand, it before using this method transfer graphene, needs to carry out graphene/copper foil
Oxidation processes make to generate copper oxide separation layer between graphene and substrate copper foil, to reduce between graphene and copper foil
Stress can more fully remove graphene.In addition, during shifting graphene, to the PVP/PVA/ graphite under stripping
Alkene film has carried out the pre-heat treatment, keeps the film just removed naturally smooth, then immerse in the absolute ethyl alcohol of warm with target substrate into
Row combines, and the step is most important to the quality for shifting graphene.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (2)
1. a kind of novel C VD graphenes dry method transfer method, which is characterized in that include the following steps：
S1, PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol) colloid are prepared；
PVP glue：1g PVP white powders are weighed, 1ml deionized waters are added, then 2ml NVP (n- vinyl pyrroles are added thereto
Ketone), absolute ethyl alcohol is eventually adding to 10ml, and hand operated mixing seals, 0 DEG C of -4 DEG C of Cord blood to being completely dissolved；
PVA glue：1g PVA white powders are weighed, 10ml deionized waters are added, are placed on magnetic stirring apparatus, temperature setting 80
DEG C, mixing time 1h is in sticky glue until being completely dissolved, and sealing, room temperature preserve；
S2, in order spin coating colloid；
Graphene/copper foil of size needed for clip, puts it into closed deionized water, after 50 DEG C of heating water bath 3h,
It takes out, the PVP glue and PVA glue obtained by spin coating successively in its graphene face, baking oven drying；
S3, the PVA/PVP/ graphenes of gained/copper foil is taken out, PVA/PVP/ graphene films is removed, then by the thin of stripping
Among film transfer to the transparent glass slide of two panels, 75 DEG C of preheating 90s, make film unfold naturally on hot plate；
S4, transfer graphene
Naturally the PVA/PVP/ graphene films unfolded are immersed in 50 DEG C of absolute ethyl alcohol and is taken out after 5s, after being adhered to cleaning
Substrate on, wait for being placed in 10min in 75 DEG C of vapor after natural drying, at this time film and substrate secure adhesion, be placed in baking oven
Drying, 110 DEG C, time 10min of oven temperature obtain PVA/PVP/ graphenes/substrate；
S5, it removes photoresist
PVA/PVP/ graphenes/substrate is taken out, 10min-15min in 75 DEG C of deionized water is placed in, removes PVA/PVP colloids
Afterwards, it is placed in deionized water and cleans 5 times, be placed in baking oven, dry, you can.
2. a kind of novel C VD graphenes dry method transfer method as described in claim 1, which is characterized in that the step S2 tools
Body includes the following steps：
Graphene/copper foil of size needed for S21, clip, puts it into closed deionized water, uses 50 DEG C of heating water bath 3h
Afterwards, it takes out, the PVP glue in its graphene face as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：1000 turns of low speed/
Minutes 6s, 2000 revs/min of time 30s of high speed, spin coating 2 times transfer them to hot plate drying, hot plate temperature after spin coating
75 DEG C of degree, time 90s；
S22, by the PVA glue on the PVP glue after drying as obtained by sol evenning machine spin coating, sol evenning machine parameter is set as：Low speed 1000
Rev/min time 6s, 4000 revs/min of time 30s of high speed, spin coating 1 time transfer them to baking oven drying, dry after spin coating
110 DEG C of box temperature degree, time 15min.
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| CN109516454A (en) * | 2018-12-14 | 2019-03-26 | 清华大学 | A kind of graphene transfer method |
| GR1009757B (en) * | 2018-12-31 | 2020-06-01 | Ιδρυμα Τεχνολογιας Ερευνας/Ινστιτουτο Επιστημων Χημικης Μηχανικης (Ιτε/Ιεχμη) | Protection of artworks with bi-dimensional materials such as graphene |
| CN114195142A (en) * | 2020-09-17 | 2022-03-18 | 香港城市大学深圳研究院 | Graphene transfer method based on stripping of polymer support material by alcohol solvent |
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| CN114195142A (en) * | 2020-09-17 | 2022-03-18 | 香港城市大学深圳研究院 | Graphene transfer method based on stripping of polymer support material by alcohol solvent |
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