CN107057041B - A kind of preparation method of the organic poly- naphthalene thermal electric film of large area narrow band gap - Google Patents
A kind of preparation method of the organic poly- naphthalene thermal electric film of large area narrow band gap Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the poly- naphthalene thermal electric film of large area narrow band gap.This method comprises the following steps: (1) tetracarboxylic acid dianhydride being placed in the quartz boat of both ends open, quartz boat is placed in quartz ampoule again, then quartz ampoule is placed in dual temperature area vacuum tube furnace, and the position of the quartz boat is made to be in the middle part of the first warm area；Substrate is placed in the carrier gas stream downstream side in the quartz ampoule and being in the quartz boat simultaneously；(2) to the dual temperature area electron tubes type stove evacuation, it is passed through carrier gas while keeping vacuum degree, controls certain heating rate, reach the certain time kept the temperature after two different target temperatures of warm area, rear Temperature fall.Vacuum degree is kept at the same time and is opened carrier gas and is controlled certain flow.Equipment needed for the method for the present invention is simple, and process is simple, energy saving, and raw material is simple and easy to get, low in cost, overcomes the difficulty of the large area synthesis of narrow band gap class grapheme material.
Description
Technical field
The invention belongs to Organic thermoelectric material fields, and in particular to a kind of to utilize gas phase transmission pyrolysis preparation large area narrowband
The method of the organic poly- naphthalene thermal electric film of gap.
Background technique
Physical resources necessary to energy and environment are human survivals and develop, the exploitation of green energy resource and environmental-friendly
Energy utilization patterns be basic demand that the mankind are able to long duration on home.Work as what fossil energy resource gradually decreased
Generation, various non-fossil energy such as wind energy, water energy, geothermal energy, nuclear energy and solar energy etc. are increasingly becoming the energy totally supplies one
Part.Thermoelectric material also gradually causes the concern of people as a kind of energy conversion material of environment-friendly type.Seebeck effect, Paar
It pastes effect and Thomson effect and provides theories integration for the application of thermoelectric material.At present Organic thermoelectric material because have source it is wide,
It is at low cost, toxicity is low, thermal conductivity is low, large area the features such as preparing flexible device can have good research and application prospect.
Low-dimensional materials are reported in terms of the electric heating transmission of Pyroelectric response with certain regulating and controlling effect.Nano material is low
Quantum local effect can be shown under dimension state, can reduce thermal conductivity while keeping conductivity to improve thermoelectricity transmission
Property, therefore the thermoelectric figure of merit of material can be improved.Such as width is less than the graphene nanobelt (Graphene of 10nm
Nanoribbons, GNRs) it is regarded as with nearly one-dimensional structure.The preparation of graphene nanobelt is divided into method " from top to bottom ",
Such as anodic oxidation of side cut-away multi-walled carbon nanotube, plasma etching, atomic force microscope etc.；With " method from bottom to top ",
Refer mainly to chemical synthesis.In spite of so many preparation method, it is desirable to the graphene nano carrying material of Cheap highly effective acquisition large area
There are still huge challenges.Therefore there is the body phase thermoelectric material of similar graphene nanobelt structure and properties still to have for preparation
It is significant.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of the organic poly- naphthalene thermal electric film of large area narrow band gap.This method institute
Need equipment simple, process is simple, and energy saving, raw material is simple and easy to get, low in cost.And obtained thin-film material thermoelectricity capability
Good, the large area for developing such Organic thermoelectric material, which synthesizes, to be had a very important significance.
To achieve the goals above, the present invention passes through control using being vacuumized under inert atmosphere in double temperature-area tubular furnaces
The flow velocity of raw material position temperature and inert gas, a step are pyrolyzed to obtain poly- naphthalene film PPN, and structure is as shown in formula I, wherein n
For the natural number greater than 20.Prepared film is without special post-processing.
Specific method includes the following steps:
1) raw material tetracarboxylic acid dianhydride is placed in the quartz boat of both ends open, then the quartz boat is placed on quartz ampoule
It is interior, then the quartz ampoule is placed in dual temperature area vacuum tube furnace, according to the flow direction of air-flow, air-flow is passed through into the dual temperature area
First heating region of vacuum tube furnace is defined as the first warm area, and the second heating region is defined as the second warm area；And make the stone
The position of Ying Zhou is in the middle part of first warm area；Substrate is placed in the quartz ampoule and in the quartz boat simultaneously
Airflow downstream side；
2) to the dual temperature area electron tubes type stove evacuation, it is passed through carrier gas while keeping vacuum degree, is taken the photograph according to 2~10
The heating rate of family name degree/min heats dual temperature area vacuum tube furnace, and the temperature of the first warm area is made to reach target temperature
Degree 530~900 degrees Celsius simultaneously keep the temperature 1~6 hours, while so that the temperature of the second warm area is reached target temperature room temperature (i.e. 15-25 takes the photograph
Family name's degree)~500 degrees Celsius and keep the temperature；Then stopping heating making dual temperature area electron tubes type in-furnace temperature be down to room temperature, i.e., described
Organic poly- naphthalene thermal electric film is obtained in substrate.
Above-mentioned preparation method, the dosage of tetracarboxylic acid dianhydride can be 100~300 milligrams in step 1).The dosage meeting of raw material
Film thickness is influenced, raw material dosage is more, and the film obtained if other conditions are the same is thicker.And film thickness is to its shape
The influence of looks structure and thermoelectric property is little.
Above-mentioned preparation method, as long as the substrate that substrate described in step 1) is resistant to the step 2) heating temperature is applicable in
In the present invention.Concretely there are silicon dioxide modified silicon wafer and smooth quartz plate in silicon wafer, surface.Substrate is not necessarily to when in use
It is particularly handled, as long as conventionally cleaning up, such as uses deionized water, ethyl alcohol, acetone successively ultrasound 3
After minute washing, N is used2Drying.
The size of the substrate can be 5 × 5-20 × 30mm2；The substrate and close to substrate side quartz boat edge away from
From for 0-10cm.
Above-mentioned preparation method, vacuum degree described in step 2) are less than or equal to 450 pas.
Above-mentioned preparation method, carrier gas described in step 2) are selected as inert gas, such as nitrogen, argon gas, preferably argon gas.
The flow of the carrier gas is controlled by mass flowmenter, is controlled in 10~30 ml/mins.
Above-mentioned preparation method, in step 2), pyrolysis temperature passes through the first warm area of control and the second warm area in the first warm area
The temperature difference poly- naphthalene thermal electric film can be deposited in substrate.
It wherein, can be by the target temperature of second warm area when the target temperature of first warm area is lower than 600 degrees Celsius
Degree is set as room temperature (i.e. 15-25 degrees Celsius), i.e. the second warm area can successfully prepare poly- naphthalene thermal electric film without heating.
When the target temperature of first warm area is more than or equal to 600 degrees Celsius, the second warm area temperature of control is than the first temperature
Area's temperature is 100-300 degrees Celsius low, and preferably 200 degrees Celsius.
The target temperature of first warm area is preferably 530~600 degrees Celsius.
Above-mentioned preparation method carries out the heating in dual temperature area in step 2), the heating rate generallyd use simultaneously
It is identical.But since the target temperature of the second warm area is lower, so the second warm area can first reach target under same heating rate
Temperature.After the second warm area reaches target temperature, begin to keep the temperature, until the first temperature-raising region temperature raising and insulating process terminate, two
Warm area terminates to keep the temperature program simultaneously, then Temperature fall.Cannot stop in advance during heating the second warm area heating or
Heat preservation, is otherwise unable to get aimed thin film or property of thin film is bad.
The organic poly- naphthalene thermal electric film being prepared according to the method described above also belongs to protection scope of the present invention.
The thickness of organic poly- naphthalene thermal electric film can be 50-200nm.
Organic poly- naphthalene thermal electric film smooth surface prepared by the present invention, good mechanical property, the adhesion-tight in substrate,
Thermal stability with higher and chemical stability.
Organic poly- naphthalene thermal electric film can be used as micro thermoelectric device, microelectronics, photoelectronic thermoelectric material application.
The invention has the following beneficial effects:
(1) reaction method is simple and easy, easy to operate；Temperature Programmed Processes are set, carrier gas flux is controlled
Obtain target product；
(2) thickness of the poly- naphthalene thermal electric film of narrow band gap obtained by being controlled as adjusting the usage amount of raw material, to reach
To different tests and processing request；
(3) mechanical property of materials prepared is good, the adhesion-tight in substrate；
(4) the material thermal stability with higher and chemical stability prepared；
(5) method preparation process and equipment are simple, there is good industrial production prospect.
The present invention utilizes the poly- naphthalene thermal electric film of large area that the method that gas phase transmission is pyrolyzed conveniently and efficiently is prepared
(poly-peri-naphthalene,PPN).The method is prepared using temperature control and inert gas flow control for the first time
The poly- naphthalene thermal electric film of high-performance of smooth, uniform and that the there is similar graphene nanobelt narrowband gap structure of wide area surface.It should
Method overcomes the difficulty of the large area synthesis of narrow band gap class grapheme material, and method is simple and easy, low in cost, environment
Close friend synthesizes the large area of such thermal electric film and is of great significance.
Detailed description of the invention
Fig. 1 is embodiment 1 and embodiment 2 prepares the raw material of the poly- naphthalene thermal electric film of narrow band gap and substrate location is put and equipment
Schematic diagram.
Fig. 2 is that embodiment 1 obtains the scanning electron microscope of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
(SEM) photo.
Fig. 3 is that embodiment 1 obtains the transmission electron microscope of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
(TEM) photo.
Fig. 4 is that embodiment 1 obtains the atomic force after the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius is scratched by blade
Microscope (AFM) photo.
Fig. 5 is that embodiment 1 obtains the close red by ultraviolet-visible-of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
What outer absorption spectrum obtained can be obtained the photon energy-Tuo Ke point spectrogram of optical band gap.
Fig. 6 is that embodiment 2 obtains the close red by ultraviolet-visible-of the poly- naphthalene thermal electric film (PPN600) under 600 degrees Celsius
What outer absorption spectrum obtained can be obtained the photon energy-Tuo Ke point spectrogram of optical band gap.
Fig. 7 obtains the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius obtains with embodiment 2 600 for embodiment 1 and takes the photograph
X-ray photoelectron spectroscopy (XPS) comparison diagram of poly- naphthalene thermal electric film (PPN600) and raw material under family name's degree.
Fig. 8 be embodiment 1 obtain the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius Raman spectrum (Raman) and
Swarming figure.
Fig. 9 is that embodiment 1 obtains poly- naphthalene thermal electric film (PPN530) the thermoelectric transport properties figure under 530 degrees Celsius.
Figure 10 is the thermoelectric transport properties figure of the poly- naphthalene thermal electric film (PPN600) under 600 degrees Celsius that embodiment 2 obtains.
Figure 11 is the poly- naphthalene film sample of comparative example preparation, wherein (a) is optical photograph top view, (b) is side view angle
Comparison diagram.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
According to the flow direction of air-flow in following embodiments, air-flow is determined by the first heating region of dual temperature area vacuum tube furnace
Justice is the first warm area, and the second heating region is defined as the second warm area.Double temperature-area tubular furnace the first warm area centers used by it with
Second warm area centre distance is 35cm.
Poly- naphthalene thermal electric film (PPN530) preparation under 1,530 degree Celsius of embodiment
1. base treatment
Silicon wafer is cut into 20 × 30mm2, after then successively being washed within ultrasound 3 minutes using deionized water, ethyl alcohol, acetone, make
Use N2Drying is stand-by.
2. pyrolysis film forming
(1) by the air-flow of treated in step 1 clean silicon wafer substrate is placed in the first warm area in dual temperature area vacuum tube furnace
Catchment, at quartz boat downstream airflow edge 2cm.Weigh the stone that raw material tetracarboxylic acid dianhydride 200mg is placed in both ends open
English boat center is placed at dual temperature area the first warm area of vacuum tube furnace center.Whole device schematic diagram is as shown in Figure 1.
(2) tube furnace vacuum degree is evacuated to lower than 450 pas to system, keeps being passed through inert gas argon while vacuum degree
(flow of argon gas is controlled gas by mass flowmenter, is controlled in 30 ml/mins.).It is 2 Celsius that the first temperature-raising region temperature raising rate, which is arranged,
Degree/min, 3 hours are kept the temperature after being warming up to 530 degrees Celsius.Second warm area is without heat treatment.It is naturally cooling to after the completion of pyrolysis
Room temperature obtains poly- naphthalene thermal electric film PPN530, with a thickness of 86.3nm.
3. the characterization of poly- naphthalene thermal electric film PPN530
The poly- naphthalene thermal electric film PPN530 being pyrolyzed under 530 degrees Celsius is done into corresponding scanning electron microscope, transmission electron microscope, original
Sub- force microscope, optical band gap test, x-ray photoelectron spectroscopy, Raman Characterization and its test of thermoelectricity transmission.
Fig. 2 is that embodiment 1 obtains the scanning electron microscope of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
(SEM) photo, as can be seen from the figure the surface of PPN530 is very smooth.
Fig. 3 is that embodiment 1 obtains the transmission electron microscope of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
(TEM) photo, as can be seen from the figure the edge of film shows apparent layer structure, illustrates that thin polymer film is to grow layer by layer
's.
Fig. 4 is that embodiment 1 obtains the atomic force after the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius is scratched by blade
Microscope (AFM) photo.As can be seen from the figure the film edge presentation scratched is step-like, obtains film thickness 85nm or so, from
The available RMS value that can measure film flatness of film surface is 1.03nm or so, illustrates that pyrolysis obtains poly- naphthalene thermal electric film
The surface PPN530 is very smooth.
Fig. 5 is that embodiment 1 obtains the close red by ultraviolet-visible-of the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius
What outer absorption spectrum obtained can be obtained the photon energy-Tuo Ke point spectrogram of optical band gap.The optics of available PPN530 from figure
Band gap is 0.37eV.
Fig. 7 obtains the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius obtains with embodiment 2 600 for embodiment 1 and takes the photograph
X-ray photoelectron spectroscopy (XPS) comparison diagram of poly- naphthalene thermal electric film (PPN600) and raw material under family name's degree.It is specially C 1s in figure
High-resolution spectrogram, available four different types of carbon peaks.Wherein 1 indicate C-C and C=C (284.5eV), 2 indicate * C-C
=O or C-O (286.5eV) or π system；3 indicate O=C-O (288.4eV)；4 indicate π (289.9eV).It can see carbon
Type 3 disappears substantially after pyrolysis, this illustrates substantially completely to be broken at anhydride group, also demonstrates the generation of polymerization reaction.
Fig. 8 be embodiment 1 obtain the poly- naphthalene thermal electric film (PPN530) under 530 degrees Celsius Raman spectrum (Raman) and
Swarming figure.It can be seen from the figure that swarming result is consistent with the peak shape of graphite alkenes carbon material.
Fig. 9 is that embodiment 1 obtains poly- naphthalene thermal electric film (PPN530) the thermoelectric transport properties figure under 530 degrees Celsius.From figure
In it is found that the thermoelectricity transimission power factor of PPN530 film has reached 0.22 μ Wm of optimal value in 340K-1K-2, in 300-
Thermoelectricity capability is excellent in the test section of 400K.
Poly- naphthalene thermal electric film (PPN600) preparation under 2,600 degrees Celsius of embodiment
1. base treatment
Silicon wafer is cut into 10 × 10mm2, after then successively being washed within ultrasound 3 minutes using deionized water, ethyl alcohol, acetone, make
Use N2Drying is stand-by.
2. pyrolysis film forming
(1) clean silicon wafer substrate obtained in step 1 is placed in the airflow downstream area of the first warm area in tube furnace, apart from stone
At English boat downstream airflow edge 2cm.It weighs raw material tetracarboxylic acid dianhydride 200mg and is placed in the quartz boat center of both ends open and be placed in
At the first warm area of tube furnace center.
(2) tube furnace vacuum degree is evacuated to lower than 450 pas to system, keeps being passed through inert gas argon while vacuum degree
(flow of argon gas is controlled gas by mass flowmenter, is controlled in 20 ml/mins.).It is 2 Celsius that the first temperature-raising region temperature raising rate, which is arranged,
Degree/min, 3 hours are kept the temperature after being warming up to 600 degrees Celsius.It is 2 degrees celsius/minutes that the second temperature-raising region temperature raising rate, which is arranged, is warming up to
40 minutes 4 hours are kept the temperature after 400 degrees Celsius.It is simultaneously stopped heat preservation after the completion of pyrolysis, room temperature is then down to naturally and obtains poly- naphthalene heat
Conductive film PPN600, with a thickness of 101.5nm.
3. the characterization of poly- naphthalene thermal electric film PPN600
The poly- naphthalene thermal electric film PPN600 being pyrolyzed under 600 degrees Celsius of preparation is done into corresponding structure and performance is surveyed
Examination.
Fig. 6 is that embodiment 2 obtains the close red by ultraviolet-visible-of the poly- naphthalene thermal electric film (PPN600) under 600 degrees Celsius
What outer absorption spectrum obtained can be obtained the photon energy-Tuo Ke point spectrogram of optical band gap.The optics of available PPN600 from figure
Band gap is 0.36eV.
Figure 10 is that embodiment 2 obtains poly- naphthalene thermal electric film (PPN600) the thermoelectric transport properties figure under 600 degrees Celsius.From figure
In it is found that the thermoelectricity transimission power factor of PPN600 film has reached 0.42 μ Wm in 370K-1K-2, in the survey of 300-400K
It is excellent to try thermoelectricity capability in section.
Comparative example:
It is compared with embodiment 2, the second warm area of setting does not heat up the case where being still within room temperature.It is real in Figure 11 (a)
It applies the poly- naphthalene film (sample is left) that example 2 obtains under 600 degrees Celsius and is heated to 600 degrees Celsius with only the first warm area, the second warm area is not
Heating obtains the optical photograph top view of substance (sample is right).Figure 11 (b) is the comparison diagram of side view angle.It can be seen that the
When two warm areas do not heat, substrate surface is covered by black powder substance, can not obtain smooth poly- naphthalene thermal electric film.
Such powdered rubber can not obtain significant thermoelectric property and application.Therefore the limit temperature of the second warm area of explanation is to high temperature
Poly- naphthalene film formation under (being not less than 600 degrees Celsius) is very necessary.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (6)
1. a kind of preparation method of organic poly- naphthalene thermal electric film, includes the following steps:
1) raw material tetracarboxylic acid dianhydride is placed in the quartz boat of both ends open, then the quartz boat is placed in quartz ampoule,
Then the quartz ampoule is placed in dual temperature area vacuum tube furnace, it is according to the flow direction of carrier gas, air-flow is true by the dual temperature area
First heating region of empty tube furnace is defined as the first warm area, and the second heating region is defined as the second warm area；And make the quartz
The position of boat is in the middle part of first warm area；Substrate is placed in the load in the quartz ampoule and being in the quartz boat simultaneously
Gas airflow downstream side；
2) to the dual temperature area electron tubes type stove evacuation, it is passed through carrier gas while keeping vacuum degree, it is Celsius according to 2 ~ 10
Degree/min heating rate dual temperature area vacuum tube furnace is heated, so that the temperature of the first warm area is reached target temperature
It 530 degrees Celsius and keeps the temperature, the temperature of the second warm area is made to reach target temperature room temperature and keeps the temperature；Then stopping heating keeping dual temperature area true
Blank pipe formula in-furnace temperature is down to room temperature, i.e., obtains organic poly- naphthalene thermal electric film on the substrate.
2. according to the method described in claim 1, it is characterized by: the dosage of tetracarboxylic acid dianhydride described in the step 1) is
100 ~ 300 milligrams.
3. method according to claim 1 or 2, it is characterised in that: substrate described in the step 1) is described to be resistant to
The substrate of step 2 heating temperature；The size of the substrate is the mm of 5 × 5-20 × 302；The institute of the substrate and close substrate side
The distance for stating quartz boat edge is 0-10 cm.
4. according to the method described in claim 3, it is characterized by: substrate described in the step 1) is silicon wafer, surface modification
The silicon wafer of silica or flat quartz plate.
5. according to the method described in claim 1, it is characterized by: vacuum degree described in the step 2 is less than or equal to 450 pas；
Carrier gas described in the step 2 is inert gas；The flow of the carrier gas is 10 ~ 30 ml/mins.
6. according to the method described in claim 1, it is characterized by: in the step 2, first warm area and the second warm area
It starts simultaneously at heating, be simultaneously stopped heat preservation, and heating rate is identical；The soaking time of first warm area is 1-6 hours.
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| CN111430530B (en) * | 2020-04-16 | 2022-09-23 | 中南林业科技大学 | Thermoelectric device based on porphin-graphene nanoribbon coupling |
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| JP2009179794A (en) * | 2007-11-20 | 2009-08-13 | Toyota Motor Corp | Method of producing polyperinaphthalene-based polymer and polyperinaphthalene-based derivative |
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| JPH07258391A (en) * | 1994-03-25 | 1995-10-09 | Res Dev Corp Of Japan | Production of thin polyperinaphthalene film |
| JP2009179794A (en) * | 2007-11-20 | 2009-08-13 | Toyota Motor Corp | Method of producing polyperinaphthalene-based polymer and polyperinaphthalene-based derivative |
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