CN101777624B - Tert-butyl isonitrile platinum nano-micro wire-based photoelectric device and preparation method - Google Patents
Tert-butyl isonitrile platinum nano-micro wire-based photoelectric device and preparation method Download PDFInfo
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- CN101777624B CN101777624B CN2010100308461A CN201010030846A CN101777624B CN 101777624 B CN101777624 B CN 101777624B CN 2010100308461 A CN2010100308461 A CN 2010100308461A CN 201010030846 A CN201010030846 A CN 201010030846A CN 101777624 B CN101777624 B CN 101777624B
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Abstract
The invention belongs to the field of organic/complex photoelectric materials and devices, and relates to a photoelectric device based on a cis- di(cyano)-di(tert-butyl isonitrile) platinum nano-micro wire and a preparation method thereof. The photoelectric device consists of a silicon substrate, a silicon dioxide insulating layer, an interdigitating electrode and a cis- di(cyano)-di(tert-butyl isonitrile) platinum nano-micro wire in turn, wherein the nano-micro wire grows in the direction vertical to the orientation of the interdigitating electrode. Simple solution processing is used in the preparation process of the device so as to avoid the traditional complex methods such as vacuum evaporation, sputtering, vacuum gas phase deposition and the like. The orientation controllable nano-micro wire can be obtained by adjusting the inclination angle of the substrate. The device of the invention has stronger optical switch function, has sensitive, reversible and stable electrical signal response to the solvent atmosphere such as methanol, acetonitrile and the like, and can be used as a sensor of the solvent atmosphere.
Description
Technical field
The invention belongs to organic and devices field, be specifically related to a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire and preparation method thereof.
Background technology
The photoconductive organic semiconductor material is at organic electroluminescent, field-effect transistor, solar cell, the optical conductor device and the various fields such as micron transducer of receiving have a wide range of applications, especially the organic nano and micro materials of one dimension: nano wire for example, nanometer rods etc. show in the semiconductor device of functionalization more outstanding (J.Phys.Chem.B, 2004,108,9574, Angew.Chem.Int.Ed.2005,44,1395 and Nature, 2001,409,66).The method for preparing the organic semiconductor nano-micro wire has a lot, but all can not control the orientation of its growth mostly, thereby can not effectively utilize material.Recently, there are some to receive the report (Adv.Mater.2006 of micron devices about organic functions, 18,3010 and Angew.Chem.Int.Ed.2007,46,1071), though utilize the nano wire of one dimension to prepare function element, complexity such as but majority has adopted vacuum evaporation, vapour deposition and the method that is difficult to parallel repetition, and the orientation of nano wire is uncontrolled in the large scale.So, how to utilize a kind of simple to operately, the controlled nano-device of method preparation orientation realizes that then its function is a very important problem fast.In addition, the organic nano and micro materials of one dimension owing to environment to external world for example chemistry, light, heat etc. have response and are used in chemical sensor and the light shutter device.But at present considerably less to the transducer of poisonous chemical solvent methyl alcohol, acetonitrile etc., and all be the change in fluorescence of utilizing relative complex, non-reversible devices such as absorption variation detect, and prepare a kind of detection simply, sensitive, reversible, stable device is the key issue with application prospect.
Summary of the invention
The present invention utilizes the solution processing mode, only need by the concentration of regulator solution and the angle of inclination of substrate, the speed of control solvent evaporates, can obtain being orientated the photoelectric device that controlled cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) (its structural formula is as follows) nano-micro wire constitutes, the character that it has photoresponse (optical switch) and methyl alcohol, acetonitrile equal solvent atmosphere is had electric response etc.
The present invention has utilized the processing of simple solution in the preparation of devices process, avoided complicated methods such as traditional vacuum evaporation, sputter, vacuum vapor deposition.By regulating the angle of inclination of substrate in solution, just can obtain being orientated controlled cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire.Concentration by regulator solution can obtain different cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of size (diameter and length).The present invention utilizes cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) of this simple method preparation to receive micron devices, has stronger light switch function, and methyl alcohol, acetonitrile equal solvent atmosphere there are sensitivity, reversible, stable electric response, can make the transducer of solvent atmosphere.
The objective of the invention is to be achieved through the following technical solutions.On at the bottom of the silicon wafer-based, prepare a layer insulating by thermal oxidation, and on insulating barrier, utilize mask plate evaporation simple substance gold as the electrode that conducts electricity, again by solvent evaporation method on electrode growth of vertical in the nano-micro wire of electrode orientation, then prepared photoelectric device, and functions such as its optical switch, solvent response have been tested based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire.
Photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of the present invention, it is characterized in that: be made up of silicon base, silicon dioxide insulating layer, slotting finger electrode, cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire successively, cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire is perpendicular to the direction growth of inserting the finger electrode orientation.
Photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of the present invention, its preparation process is as follows:
1, with silicon chip as substrate, in substrate, prepare the silicon dioxide insulating layer of 200～300 nanometers by thermal oxidation process;
2, having on the silicon chip of silicon dioxide insulating layer, utilization is mask plate with the figure of slotting finger electrode shape complementarity, the metallic gold of the crome metal of evaporation 10～20 nanometers and 30～40 nanometers successively, and then to obtain having between finger distance be that 10～20 microns, finger widths are the silicon base in 5～8 microns slotting finger-like gold electrode district;
3, will have the silicon base of inserting finger-like gold electrode district tilts to put into the container of the good methanol solution that fills cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) of configured in advance behind 40～50 degree angles in the horizontal direction, closed container, and then inserting the growth of carrying out cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire in the finger-like gold electrode district;
4, treat that the slow volatilization of methyl alcohol is after 2～5 days, insert finger-like gold electrode district and can partly expose liquid level, be covered with green one dimension wire solid thereon, can stop growing, take out substrate, thereby prepare photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire.
Use the CHI630C electrochemical workstation that the opto-electronic device for preparing is carried out the conductivity test, when being added to the voltage constant of inserting in the finger-like gold electrode district, utilize xenon lamp and monochromator to regulate and be radiated at, can obtain the optical switch character curve of device based on light intensity and emission wavelength on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) the nano-micro wire photoelectric device; When voltage constant, feed solvent atmosphere by carrier gas system, can obtain the curve that the signal of telecommunication changes with solvent atmosphere.
The preparation of inserting finger-like gold electrode district is at condition of high vacuum degree (2 * 10
-4～5 * 10
-4Pa air pressure) under, utilize the method for traditional vacuum evaporation to obtain, the chromium of first evaporation 10～20 nanometers is for gold is adhered in that substrate surface is more effective before gold evaporation, and gold electrode comes off after preventing from electrode immersed solution.
The concentration (1 * 10 of the methanol solution by changing cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II)
-4～2 * 10
-3Mol), can obtain diameter (0.2～0.5 micron) and the different nano-micro wire of length (100～400 microns).For example, the concentration when the methanol solution of cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is 2*10
-3During mol, utilize said method can obtain length and be about the micro wire that 400 micron diameters are about 0.4 micron.Owing to insert finger-like gold electrode district very little (3 millimeters), under the states of 40～50 degree that tilt especially only less than 2 millimeters height, therefore, in the process of solvent evaporates, the change in concentration of inserting finger-like gold electrode district high and low position place cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) methanol solution is little, to the almost not influence of growth of device surface nano-micro wire.Xenon lamp and monochromator not only emission wavelength are controlled, can also use the luminous intensity tester light intensity that it sends is tested.Need to prove, same device preparation method and method of testing not only can be used in the preparation and test of cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire photoelectric device, can also be used in the preparation and test based on the photoelectric device of other organic photoelectric functional materials, as phthalocyanine, porphyrin and Graphene etc.
Description of drawings
Fig. 1: the structural representation of photoelectric device of the present invention;
Wherein each component names is: silicon base 1, silicon dioxide insulating layer 2, insert finger-like gold electrode district 3, perpendicular to the nano-micro wire 4 of electrode orientation growth;
Fig. 2: the electric current-time optical switch character curve of photoelectric device of the present invention under the illumination of different wave length;
Fig. 3: photoelectric device of the present invention is to the signal of telecommunication sensing curve of methyl alcohol atmosphere;
Fig. 4: photoelectric device of the present invention is to the signal of telecommunication sensing curve of acetonitrile atmosphere.
Embodiment
The present invention is further elaborated below in conjunction with embodiment, rather than will limit the invention with this.
Embodiment 1: preparation cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is received the test of micron photoelectric device and optical switch character
1, preparation cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is received a micron photoelectric device
As substrate, in substrate, obtain the silicon dioxide insulating layer of 300 nanometers with silicon chip by thermal oxidation.At condition of high vacuum degree (5*10
-4The Pa atmospheric pressure) under, having on the silicon chip of silicon dioxide insulating layer, utilization is mask plate with the figure of slotting finger electrode shape complementarity, the crome metal of evaporation 15 nanometers and the metallic gold of 35 nanometers, distance is 10 microns between finger, finger beam is 5 microns, and the width of electrode district (d) is 3 millimeters, has obtained having the substrate of inserting finger-like gold electrode district.Configuration concentration is 2*10 in closed container
-3The methanol solution of cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) of mol is put into this container with substrate inclination 45 degree of making, and closed container is treated its slow volatilization.Volatilization through the long period (about 2 days), observing electrode partly exposes outside the liquid level, (length is about 400 microns to be covered with cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano wire on it, diameter is about 0.4 micron), can open container, stop growing, take out substrate, just obtained photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire.The structural representation of device as shown in Figure 1.
2, cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is received the open the light mensuration of character of micron devices light
With electrochemical workstation the device of making is carried out the conductivity test, utilize xenon lamp and monochromator to regulate to be radiated at cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) to receive light intensity and emission wavelength on the micron devices, when the voltage constant at device two ends, test its electric current-time graph.Respectively two parts in the slotting finger electrode district on the device are inserted the positive and negative polarities of electrochemical workstation respectively, the voltage that setting is added in the device two ends is 0.5 volt, under the state of dark, electric current is along with the straight line that is varied to of time, shown among Fig. 2 0～50 second at this moment; The incident illumination that as wavelength is 400 nanometers is when device surface, and electric current moment of device strengthens, shown among Fig. 2 50～100 seconds; And the intensity when electric current is got back to dark attitude when closing incident light.Regulate the irradiation (opening) of incident light like this and close (pass), just obtained optical switch curve shown in Figure 2, device has been realized light switch function.And the irradiates light (400～600 nanometer) of adjusting different wave length, the degree of current response is also different, and as can be seen, wherein when wavelength was 450 nanometers, electric current strengthened maximum, strengthened less when wavelength is 600 nanometers in Fig. 2.What deserves to be mentioned is that through the experiment of No. 4 switch light sources, above-mentioned device shows very fast response speed and goodish stability and repeatability.
Embodiment 2: cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is received the sensing determination of micron devices to methyl alcohol atmosphere
1, prepares cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) with embodiment 1 step 1 method and receive micron devices.
2, with electrochemical workstation the device of making is carried out the conductivity test, under nitrogen environment, as carrier gas, the control flow velocity is 400cm with nitrogen
3/ min, methanol solvate atmosphere is led to device surface under the blowing of nitrogen, the feeding of controlled atmospher and stopping, can test component to the electric response (Fig. 3) of methyl alcohol.Respectively two electrodes on the device are inserted the positive and negative polarities of electrochemical workstation, it is 0.5 volt that the voltage that is added in the device two ends is set, and under the state that has only nitrogen to feed, electric current is along with the straight line that is varied to of time, shown among Fig. 3 0～50 second at this moment.When the nitrogen that has methyl alcohol blew at device surface, electric current moment of device strengthened, and shown among Fig. 3 50～100 seconds, and the electric current that is blown into when having only nitrogen that stops methyl alcohol being got back to original intensity.Regulate the feeding (opening) of methyl alcohol like this and close (pass), just obtained methanol solvate electric response curve shown in Figure 3, device has been realized the sensing function of methanol solvate like this.What deserves to be mentioned is that through the multiple switching experiment, above-mentioned device shows very fast response speed and goodish stability and repeatability.
Embodiment 3: cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is received the sensing determination of micron devices to acetonitrile atmosphere
1, prepares cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) with embodiment 1 step 1 method and receive micron devices.
2, with electrochemical workstation the device of making is carried out the conductivity test, under nitrogen environment, as carrier gas, the control flow velocity is 400cm with nitrogen
3/ min, acetonitrile solvent atmosphere is led to device surface under the blowing of nitrogen, the feeding of controlled atmospher and stopping, can test component to the electric response (Fig. 4) of acetonitrile.Respectively two electrodes on the device are inserted the positive and negative polarities of electrochemical workstation, it is 0.5 volt that the voltage that is added in the device two ends is set, and under the state that has only nitrogen to feed, electric current is along with the straight line that is varied to of time, shown among Fig. 4 0～50 second at this moment.When the nitrogen that has acetonitrile blew at device surface, electric current moment of device weakened, and shown among Fig. 4 50～100 seconds, and the electric current that is blown into when having only nitrogen that stops acetonitrile being got back to original intensity.Regulate the feeding (opening) of acetonitrile like this and close (pass), just obtained acetonitrile solvent electric response curve shown in Figure 4, device has been realized the sensing function of acetonitrile solvent like this.What deserves to be mentioned is that through the multiple switching experiment, above-mentioned device shows very fast response speed and goodish stability and repeatability.
Claims (7)
1. photoelectric device based on structural formula cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire as follows, it is characterized in that: form by silicon base, silicon dioxide insulating layer, slotting finger electrode, cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire successively, cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire is perpendicular to the direction growth of inserting the finger electrode orientation
2. the preparation method of the described a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of claim 1, its preparation process is as follows:
1) with silicon chip as substrate, in substrate, prepare the silicon dioxide insulating layer of 200～300 nanometers by thermal oxidation process;
2) having on the silicon chip of silicon dioxide insulating layer, utilization is mask plate with the figure of slotting finger electrode shape complementarity, the metallic gold of the crome metal of evaporation 10～20 nanometers and 30～40 nanometers successively, and then to obtain having between finger distance be that 10～20 microns, finger widths are the silicon base in 5～8 microns slotting finger-like gold electrode district;
3) will have the silicon base of inserting finger-like gold electrode district tilts to put into the container of the good methanol solution that fills cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) of configured in advance behind 40～50 degree angles in the horizontal direction, closed container, and then inserting the growth of carrying out cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire in the finger-like gold electrode district;
4) treat that the slow volatilization of methyl alcohol is after 2～5 days, insert finger-like gold electrode district and can partly expose liquid level, be covered with green one dimension wire solid thereon, can stop growing, take out substrate, thereby prepare photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire.
3. the preparation method of a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire as claimed in claim 2, it is characterized in that: crome metal and metallic gold are 2 * 10
-4～5 * 10
-4Method by vacuum evaporation under the Pa air pressure prepares.
4. the preparation method of a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire as claimed in claim 2, it is characterized in that: the concentration of the methanol solution of cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) is 1 * 10
-4～2 * 10
-3Mol.
5. the described a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of claim 1 is in the application aspect the solvent atmosphere transducer.
6. a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire as claimed in claim 5 is characterized in that: as methyl alcohol, acetonitrile solvent atmosphere sensor in the application aspect the solvent atmosphere transducer.
7. the described a kind of photoelectric device based on cis two (cyano group)-two (tert-butyl group isocyanide) platinum (II) nano-micro wire of claim 1 is in the application aspect the optical switch.
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