KR101851339B1 - Method of fabricating high quality black phosphorous thin film by the treatment of oxide-layer removal and reactive oxygen reaction - Google Patents
Method of fabricating high quality black phosphorous thin film by the treatment of oxide-layer removal and reactive oxygen reaction Download PDFInfo
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- KR101851339B1 KR101851339B1 KR1020150172253A KR20150172253A KR101851339B1 KR 101851339 B1 KR101851339 B1 KR 101851339B1 KR 1020150172253 A KR1020150172253 A KR 1020150172253A KR 20150172253 A KR20150172253 A KR 20150172253A KR 101851339 B1 KR101851339 B1 KR 101851339B1
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- H—ELECTRICITY
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- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02543—Phosphides
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- H—ELECTRICITY
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
- H01L21/205—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy using reduction or decomposition of a gaseous compound yielding a solid condensate, i.e. chemical deposition
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/702—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof of thick-or thin-film circuits or parts thereof
- H01L21/707—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof of thick-or thin-film circuits or parts thereof of thin-film circuits or parts thereof
Abstract
The present invention relates to a method for producing a black thin film and a black thin film produced therefrom, and more particularly to a method for forming a black thin film by using active oxygen in a chamber and removing the accompanying black oxide film through a water washing step, . More specifically, the black ultra thin film of the present invention can have high applicability to optoelectronic devices and field effect transistors by virtue of having a substantially flat surface without a defect in a large area and having a surface roughness characteristic of 1 nm or less.
Description
The present invention relates to a method for producing a black thin film and a black thin film produced therefrom, and more particularly to a method for forming a black thin film by using active oxygen in a chamber and removing the accompanying black oxide film through a water washing step, . More specifically, the black ultra thin film of the present invention can have high applicability to optoelectronic devices and field effect transistors by virtue of having a substantially flat surface without a defect in a large area and having a surface roughness characteristic of 1 nm or less.
In order to realize future wearable electronic devices and transparent displays, it is necessary to develop electronic devices that are bent and stretched but have excellent performance.
Since silicon, two-dimensional materials such as graphene and molybdenum disulfide are considered as materials for making next-generation electronic devices. Recently, black phosphorus (black phosphorus), which is evaluated as a substitutable material for graphene, As the allotropic substance, it is a material similar in shape to graphite, including a metallic luster in a retraction color.
In particular, since graphene has a shortage of direct electron band gap between a valence band and a conduction band, there is a limit to substitute a representative semiconductor, silicon. On the other hand, a black band not only has a direct bandgap but also can control a bandgap according to thickness It has the advantage of being able to operate in a wide wavelength range from visible light to near-infrared light.
The band gap is a physical quantity inherent to the material, and the current easily flows as a conductor to become a conductor. As the value becomes larger, the current does not easily flow and becomes an insulator. Therefore, if the size of the bandgap can be freely controlled, it is possible to manipulate the electrical properties of the material from conductor to insulator.
In order to lower the operating voltage of the transistor and to reduce the heat generated, it is necessary to design a very thin transistor at the atomic level, which is the next generation material that can meet this demand. When black phosphorus is put to practical use, a high-performance semiconductor with an electron migration speed much faster than conventional silicon semiconductors can be realized.
However, since the reaction speed of air in black is high, it is not stable and natural oxide film is formed. This causes a problem of deterioration of the electronic device characteristics by inhibiting current flow on the surface or interface of the black oxide with time, An effective oxide film removing method is necessarily required.
On the other hand, a black phosphor having a bulk band energy of about 0.3 eV has a high photoluminescence characteristic through direct transition regardless of the thickness, and it is possible to control the variable band energy from the near infrared to the visible light region below 3 nm. At present, it is possible to form a black thin film by a mechanical peeling method. However, this method has a great difficulty in manufacturing a black thin film due to the formation of a native oxide film.
Disclosure of the Invention The present invention has been conceived to solve the above-mentioned problems. It is an object of the present invention to provide a chamber for forming an ultra thin film of black phosphor having a high reaction rate with air, and a black thin film is etched through active oxygen generated by the reaction of oxygen and ultraviolet A method of forming a black ultra thin film and treating it with water to remove the black oxide film of the ultra thin black film.
One aspect of the present invention relates to a method of manufacturing a black thin film for removing a black oxide film by treating a black thin film with water, wherein the black thin film is formed by a method of mechanically peeling from a pure black pristine or a chemical vapor deposition method Which may be a black thin film.
In one embodiment of the present invention, the black thin film is etched by active oxygen in a chamber to produce a black ultra thin film, and the active oxygen may be generated through reaction of ultraviolet rays and oxygen in the chamber.
As one embodiment of the present invention, the black ultra thin film produced by the above-described method can have a surface roughness of 1 nm or less in an area of 10 탆 x 10 탆.
In one embodiment of the present invention, the black thin film may be a black ultra thin film having a thickness of 3 nm or less. In one embodiment of the present invention, the black ultra thin film has one or two photoluminescence (PL) peaks at a wavelength of 700 to 1000 nm, a single PL peak by a black atomic monolayer at 780 to 830 nm and 880 Lt; / RTI > to 950 nm and a single PL peak by a black bidentate layer at 950 nm. As one embodiment of the present invention, the present invention relates to an optoelectronic device including the black ultra thin film.
In one embodiment of the present invention, the black ultra thin film may have a surface roughness of 1 nm or less and a thickness of 8 nm or more at an area of 10
The present invention can provide a black thin film having excellent electric device characteristics by surface cleaning of a black thin film. Further, the present invention can be applied to an optoelectronic device including a photodiode, a light emitting diode, a solar cell, a photodetector, and an optical switch using the photoluminescence property of a black thin film, (field effect transistor).
1 illustrates a method for producing a black thin film of the present invention.
2 shows an optical image of the black thin film of the present invention.
Fig. 3 shows the surface morphology measured by an AFM (Automic Force Microscope) of the black thin film of the present invention.
4 shows Raman spectra of a black thin film according to the UV irradiation time of the present invention.
5 is a graph showing the peak difference of the Raman spectrum of the present invention.
6 shows the PL (Photoluminescence) spectrum of the monatomic layer, the two-atom layer, and the black thin film of the present invention.
7 is a graph showing the electrical characteristics of the black thin film of the present invention.
8 is an optical image of a transistor device manufactured using the black thin film of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention. Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, The description of the known function and configuration will be omitted.
In the term of the present invention, a pure black (pristine) means a black crystal in a bulk crystalline state.
In the term of the present invention, a black thin film refers to a thin film prepared from a pure black pristine including a mechanical, physical or chemical method.
In the term of the present invention, the term " black ultra thin film " means an ultra thin film prepared by etching a black thin film by active oxygen to adjust its thickness. Specifically, it may include a black ultrathin film having a thickness of 3 nm or less, a black ultrathin film having a thickness of 3 nm to 8 nm, and a black ultrathin film having a thickness of 8 nm or more, which can be applied to a field effect transistor, . Preferably, the thickness of the black ultra thin film of 8 nm or more may be 100 nm or less, more preferably 50 nm or less, and 30 nm or less may be more preferable for an ultra thin film device.
The present invention relates to a method for producing a black thin film having excellent surface characteristics and a black thin film produced by the method.
The black phosphorus of the present invention is a black phosphorus, which has the same phosphorus elements but different properties, including a metallic luster in a retraction color and a surface similar in shape to graphite. Black is a semiconducting material composed of several layers of phosphorus and is layered like a graphene. Black is attracting attention as a next-generation semiconductor material to replace graphene, which has no bandgap and is difficult to control current flow.
Since the bandgap can be adjusted according to the thickness of the black phosphor, it can operate in a wide wavelength range from visible light to near infrared light and exhibits excellent photoresponsivity and electron mobility of 1000 cm 2 / Vs or more .
Black has a direct band gap property, and the band gap can be adjusted to about 0.3 to 1.5 eV depending on the thickness. A thin black thin film of 3 nm or less in thickness is advantageous in applications of optoelectronic devices because of its excellent variable light emission characteristics and is excellent in application of field effect transistors because of its excellent electron mobility when it is 8 nm or more.
The black thin film used as a base material for preparing the black ultra thin film of the present invention may be one prepared from a pure black pristine including a mechanical, physical or chemical method.
Specifically, the black thin film of the present invention can be manufactured by a manufacturing method described below, but not limited thereto, and may include a mechanical, physical, or chemical method if it is a known method of producing a black thin film from pure black pristine , It is needless to say that the above-described methods can be applied independently and combinedly. Likewise, the method of manufacturing a black thin film should be construed as applying all of the following embodiments or examples in which two or more aspects are derived in combination, and for a clearer understanding, any one aspect and / or two or more aspects These contents, which apply to both the combined examples, are collectively referred to as general aspects of the present invention and can be described in detail.
In one embodiment of producing a black thin film, a mechanical exfoliation method may be a method of separating black phosphorus into layers by using a pure black pristine adhesive material, and specifically, using a scotch tape or the like, As shown in Fig.
In another embodiment for producing a black thin film, it may include a solvent peeling method in which pure black pristine is dispersed and removed in a solvent. The solvent stripping method may include a method of producing a black thin film by mixing a pure pristine into a solvent to prepare a dispersion, stirring the dispersion or irradiating ultrasound to strip pure pristine . The solvent may be selected from alcohols and aprotic solvents. The alcohols may be at least one alcohol selected from C1 to C8. Examples of the aprotic solvent include tetrahydrofuran, hexane, methylene chloride, At least one selected from the group consisting of toluene can be used. The dispersion containing the peeled black thin film may be subjected to separation of the solvent through known means such as filtration and centrifugation, and then a black thin film can be prepared.
In another embodiment for producing a black thin film, the chemical vapor deposition method is a method in which a catalyst metal is deposited on a substrate to form a thin metal film, then a black gas is flowed at a high temperature and then cooled to obtain a black thin film formed on the metal film Lt; / RTI >
Although it is possible to prepare a black thin film whose thickness is reduced from pure pristine by the mechanical, physical or chemical method, it is difficult to precisely control the thickness of the black thin film and the surface roughness of the thin film is fixed Or contains many defects. Therefore, even if a thin film of black is produced through the mechanical, physical or chemical method, the black thin film produced by the above method may not be able to control the thickness of the thin film to an ultra thin film of 3 nm or less, The application to an optoelectronic device or an electric field transistor is limited.
Accordingly, the present invention provides a method for producing a black ultra thin film and a black ultra thin film which precisely adjusts the thickness of the black thin film, minimizes the surface roughness of the thin film in a large area, and substantially does not have defects.
The black ultra thin film of the present invention means that the black thin film is prepared by etching the black thin film by the active oxygen to a desired thickness.
Since the black thin film has a high reaction rate in air and is not stable, a process for producing a black ultra thin film can be performed in a chamber. At this time, the ultra thin black film is located on the sample table formed in the chamber, and the black ultra thin film having a thin thickness can be formed by etching the black film.
When oxygen (O 2 ) gas is injected into the chamber with irradiation of ultraviolet rays, oxygen gas can be decomposed and recombined into ozone (O 3 ) and monoactive oxygen (O) by the energy of ultraviolet rays. The active oxygen is oxygen, which is chemically more reactive than oxygen, and can act as an oxidizing agent for etching the surface of the black thin film.
The formation of the black ultra thin film of the present invention can form ozone and active oxygen by the reaction of oxygen and ultraviolet rays in the chamber and can form a black ultra thin film by etching the black thin film by reactive oxygen as shown in the following reaction formula (1).
[Reaction Scheme 1]
(In the above scheme 1, O 3 (g), O 3 (ad) ozone, (BP) heukrin, O 2 (g) is O, O (g) is the active oxygen, -O (ad) is oxygen is adsorbed Black.
The etch reaction may be sequentially performed according to the surface area size of the surface defects on the black thin film. That is, a small defect of several hundreds of nanometers or less can be selectively etched by the above reaction, and a larger size can be etched away from the edge.
Substantial surface defects existing on the black thin film can be substantially removed by the sequential reaction characteristics of the etching reaction, and the surface roughness can also be precisely adjusted to the range of 1 nm or less at the area of 10 탆 x 10 탆.
The formation of the ultra thin black layer may be performed by introducing oxygen into the chamber at a rate of about 100 to 600 sccm (standard cubic centimeter per minute), and maintaining the pressure of 1 atm in the chamber. However, the present invention is not limited thereto.
The temperature inside the chamber is 15 to 45 DEG C, and the ultraviolet ray to be irradiated is 180 to 250 nm. The desired thickness can be controlled according to the irradiation amount of light, and irradiation with an output of 10 to 30 mW is performed to form a black ultra thin film Is preferably, but not limited to, a uniform reaction with no side reaction. Preferably, the chamber includes an ultraviolet ray inflow portion through which ultraviolet rays are introduced, and the inflow portion is preferably composed of quartz having an excellent transmittance. In this case, the quartz preferably has a thickness of 0.1 to 0.5 mm.
The formation of the black ultra thin film according to the present invention is advantageous in that ozone and active oxygen are directly produced by the reaction of oxygen and ultraviolet rays during the etching process of black phosphorus and the black ultra thin film is formed by using the generated ozone and active oxygen, have.
The thickness of the black ultra thin film according to the present invention may be proportional to the degree of reaction with the black phosphorus depending on the amount of generated ozone and active oxygen. The wavelength of light may range from 180 to 250 nm, and light of 189 nm may be preferred to decompose the double bonds of oxygen to produce active oxygen. As the irradiation amount of light increases or the intensity of light becomes stronger, the thickness of the black ultra thin film obtained in a unit time can be made smaller. However, the thickness of the black ultra thin film of the present invention is not obtained only at a specific irradiation amount of light, a specific intensity of light, and various combinations of the above two parameters are possible in order to obtain a specific thickness of the black ultra thin film. Of course.
The above-described chamber is only an embodiment for generating active oxygen in the present invention. However, the method of manufacturing the black thin film of the present invention is not limited thereto, and it is possible to generate active oxygen to remove the black oxide film by active oxygen The size and shape of the chamber, the supply and discharge of oxygen, and the like, and these modifications are also included in the present invention.
In one embodiment of the present invention, the black oxide film can be selectively removed from the black ultra thin film containing the oxide film generated by the active oxygen. The black oxide layer is a liquid oxide layer. In the present invention, the black oxide layer and the surface defects of the black oxide ultra thin layer can be removed by washing with water as a non-limiting example.
By treating the black ultra thin film with water, the black oxide film existing on the surface of the black ultra thin film is selectively removed, the surface is flat, and a black thin film having uniform thickness can be obtained.
In one embodiment of the present invention, the method for removing the black oxide layer may be, for example, a method of washing the black ultra thin film in water, a method of directly spraying water on the black ultra thin film, And then washing it. However, the present invention is not limited thereto.
In one embodiment of the present invention, the water used for washing may be distilled water or deionized water, but is not limited to the above examples insofar as the nature of water is maintained.
A method using the above-described cleaning device is, for example, a method of disposing a black ultrathin film on a chuck capable of rotating through a spin type cleaner, spraying water while rotating the chuck in one direction, Foreign matter can be removed.
When the black ultrathin film is contacted with water, the temperature for washing the black ultrathin film with water may be 1 to 70 ° C, and the contact time with water may be 10 to 10 hours. The black oxide film present in the black ultra thin film can be selectively removed in the temperature range of 1 占 폚 to 70 占 폚 and can be selectively removed most preferably in the temperature range of 5 占 폚 to 50 占 폚. If the temperature is out of the above range, the removal of the oxide film may not be completely performed or may be undesirably performed due to rapid etching to black. The black ultrathin film and water can remove the black oxide film at a contact time of 10 seconds to 10 hours, and can be effectively removed at a contact time of preferably 20 seconds to 5 minutes. If the contact time is exceeded, the oxide film may not be removed or may be etched to black or the process efficiency may be lowered, which may be undesirable.
In order to form a black ultra thin film, the present invention can perform the etching of the active oxygen by repeatedly etching the active oxygen after etching through active oxygen, and then irradiating ultraviolet rays again. A variety of modifications such as omitting the cleaning process are possible. Preferably, in order to produce a black ultra thin film with a thickness of 3 nm or less, the etching is rapidly performed by oxygen, moisture and light at the time of exposure to the atmosphere, so that a washing step may be added or omitted depending on the thickness of the ultra thin film. For the measurement, formation of a surface protective layer may be required.
The present invention provides a black ultra thin film produced by the above-described method.
The black ultra thin film of the present invention may be a black ultra thin film laminated from one to five layers, and may have a thickness of 3 nm or less. The ultra thin black thin film with a thickness of 3 nm or less can be applied to an optoelectronic device because of its excellent light emission or light absorption property by band gap tuning from the near infrared to the visible light region. An optoelectronic element is an element that changes light energy and electric energy, and may include a photodiode, a light emitting diode, a solar cell, a photodetector, and an optical switch.
The black ultra thin film manufactured by the present invention can be etched using an optical image, Raman or the like.
In addition, in order to confirm whether or not the etching of the black ultra-thin film is accurately performed, it is possible to confirm whether or not the etching is performed according to the time during which ultraviolet rays are irradiated.
The black ultra thin film of the present invention can be measured by Raman spectroscopy, which can be measured by a phonon according to the manner of vibration motion when the black atom has a constant lattice structure. The black ultra thin film of the present invention can measure the A 1 g mode oscillating in the direction perpendicular to the lattice plane through the Raman spectroscope and the B 2g and A 2 g modes oscillating in the direction parallel to the lattice plane.
In addition, the black ultra thin film of the present invention can measure photoluminescence (PL) characteristics. This method can measure the emission of light as the electrons of the specimen are excited and come to a steady state by using the phenomenon of emitting light by irradiating light of a specific wavelength of the specimen.
The black ultra thin film of the present invention has one or two PL peaks at a wavelength of 700 to 1000 nm and has a single PL peak by a black atomic single atom layer at 750 to 810 nm and a single PL peak by a black two atom layer at 870 to 930 nm And a PL peak including at least one selected from the group consisting of:
According to one embodiment of the present invention, a monoatomic layer and a monatomic layer of black ultra thin film can be produced, wherein the PL of the single atomic layer is measured at about 780 nm and the PL of the two atomic layer is measured at about 900 nm.
The black ultra thin film of the present invention can be applied to an optoelectronic device such as a photodiode, a light emitting diode, a solar cell, a photodetector, and an optical switch.
Also, the thickness and surface roughness of the black thin film produced by the present invention can be confirmed by using an atomic force microscope (AFM), a scanning tunneling microscope (STM) or the like.
In particular, the atomic force microscope (AFM) can measure the thickness of an exact black thin film by directly measuring the force between atoms using the tip of the tip, which is made of silicon, which is a very thin metal or semiconductor.
The surface roughness of the black ultra thin film of the present invention can be measured with an atomic force microscope (AFM), and the surface roughness can be 1 nm or less at an area of 10 탆
The black ultra thin film of the present invention may be a black ultra thin film having a thickness of 8 nm or more. When the black ultra thin film has a thickness of 8 nm or more, it has a bulk band gap of about 0.3 eV and can have excellent electron mobility. Specifically, it can have an electron mobility of 1000 cm 2 / Vs or more, And the like.
The black ultra thin film according to the present invention can be a high quality black super thin film having excellent electrical characteristics and can be applied to a field effect transistor and the like.
Hereinafter, the present invention will be described in more detail by way of examples. It should be understood, however, that the following examples are only illustrative and not intended to limit the scope of the present invention.
[Characteristic evaluation]
1. AFM measurement:
AFM (Park system XE-70) measurements were performed at room temperature with a scanning rate of 0.4 Hz. The surface roughness (roughness) was calculated by using the XEI program (version 1.6.5) purchased with the AFM equipment and the root mean squared (RMS) value of the surface step from the 3-dimensional surface image measured at the size of 10 μm × 10 μm ) Were calculated and measured.
2. Raman analysis:
Raman analysis was performed using a home-built confocal Raman system (EMCCD, Tunable Ar ion laser, 457-514 nm).
3. PL measurement method:
Nd: YAG (micro objective 40x lens) was measured at 488, 532 nm, and the laser output was measured at 0.01 mW to reduce the damage of the black ink.
[Example 1]
Black thin films were prepared by mechanically peeling pure black (99.99%, bulk elements) with scotch tape (3M) on a 285 nm thick SiO 2 / Si substrate.
For ultraviolet treatment, a black thin film was placed in a sample chamber of an optical capacity cell of 40 ml inside volume. The optical cell was equipped with a 0.17 mm thick quartz glass (077 Vitreosil® Optical Fused Quartz) through which ultraviolet light could enter. The optical cell was maintained under an O 2 gas condition of 1 sccm at 500 sccm.
UV light was irradiated by a pencil type mercury lamp (Oriel, 6035) and the lamp power was 19 mW at 200 nm. The ultraviolet irradiation time was 30 minutes to prepare a black ultra thin film.
A black thin film was formed on the SiO 2 / Si substrate and the black ultra thin film etched with active oxygen generated by ultraviolet ray irradiation was immersed in a beaker containing deionized water and then washed for 1 minute.
[Example 2]
All the steps were carried out in the same manner as in Example 1 except that the ultraviolet irradiation time was 10 minutes, to prepare a black ultra thin film.
[Example 3]
All the steps were carried out in the same manner as in Example 1 except that the ultraviolet irradiation time was 20 minutes, to prepare a black ultra thin film.
[Example 4]
All steps were carried out in the same manner as in Example 1 except that the ultraviolet ray irradiation time was irradiated for 31 minutes to prepare a black ultrathin film.
[Example 5]
All steps were carried out in the same manner as in Example 1 except that no ultraviolet ray was irradiated to prepare a black thin film.
[Example 6] Fabrication of transistor elements of black thin film
Black grain bulk crystals (99.99%, smart elements) were mechanically stripped using a scotch tape (3M) on a 285 nm thick SiO 2 / Si substrate.
We also fabricated a device for transistor measurement by electron beam lithography on a 30 nm thick black thin film.
The fabricated device was immersed in a beaker containing deionized water and then washed for 1 minute.
[Evaluation results]
2 is a result of an optical image according to Example 1 of the present invention. Also, FIG. 3 shows AFM measurement results for areas A and B in FIG. Figs. 2 (a) and 3 (d) show the ultra thin film of black ink by mechanical peeling. The image was obtained within 20 minutes after the mechanical peeling, but the surface was uneven. This roughness is attributed to the white spots due to the oxidation of the black phosphorus, and the pure rinsing of the pristine was measured to be 5.4 nm in the 5.1-nm B region in the A region.
Fig. 2B and Fig. 3E show that after the irradiation with ultraviolet light, the active oxygen reacts with the black phosphorus to form a black phosphorus oxide film, and the thickness of the black phosphorus oxide film was measured to be about 174 nm in the region B because of the high hydrophilicity of the black phosphorus It was found that the oxide film absorbed water and the thickness of the surface greatly changed. The black oxide film can be removed by deionized water, which is shown in Figure 2c and Figure 3f. The thickness change after washing in the first black state was confirmed to be about 5.5 nm, and the smooth surface of the black ultra thin film was confirmed. The surface roughness was confirmed to be 1 nm or less at an area of 10 탆
4 shows the results of the Raman spectra (A 1 g , B 2 g , A 2 g ) of the ultra-thin black films prepared in Examples 1 to 4 of the present invention. The positions of the Raman peaks of the black ultra- The change was confirmed. The peak position of the B 2g and A 2 g bands changed as the thickness of the black ultrathin film was decreased with the UV irradiation time, and the peak position of the B 2g and A 2 g bands The number of layers of the thin film can be calculated.
FIG. 5 shows the peak difference values of the B 2g and A 2 g bands of the black ultra thin film of FIG. 4 according to the UV irradiation time. When the UV irradiation time was less than 20 minutes, the thin film thickness was 8 nm or more and the peak difference value was not changed significantly. However, when the UV irradiation time was more than 20 minutes, the peak difference value increased sharply, which means that the black thin film gradually became thinner than 3 nm. At the UV irradiation time of 30 minutes, a black atom ultra thin film of a two atom layer was formed and at a UV irradiation time of 31 minutes, a black atom ultra thin film of a single atom layer was formed.
6 shows PL spectra of the black atom ultra thin films of the single atom layer and the two atom layer manufactured by Example 1. FIG. In the spectrum, two PL peaks contributed respectively by the single atom layer and the two atom layer were clearly obtained. By separating the peaks by the deconvolution method, the single atom layer and the two-atom layer ultrathin films were 782 nm and 896 nm A strong characteristic PL peak was obtained. Specifically, a strong characteristic PL peak of about 1,000 photon counts was obtained at an output of 488 nm, 0.01 mW for a two atomic layer black ultra thin film and at 60 seconds.
It is known that the black atomic layer has a median value of the PL spectrum at about 780 nm and the two atomic layer has a median value of the PL spectrum at about 900 nm so that there is no nanometer level surface defect that attenuates the PL signal size in the ultra- have.
On the other hand, the black thin film prepared only by the mechanical peeling method showed no PL spectrum, whereas the single atom layer or the two atomic layer black ultra thin film obtained by the UV irradiation and water washing of the present invention showed strong PL spectrum. Therefore, the black thin film produced by the conventional mechanical stripping method has many defects and uneven surfaces, and the single atom layer and the two-atom layer black ultra thin film of the present invention are free from defects in a large area and have a uniform surface .
7 shows an optical image of a transistor device using a 30 nm thick black thin film manufactured by Example 6. In the optical image, the formation of the black oxide layer is not confirmed. However, in the dark field image, unlike the optical image, the deionized water washing Previously, a considerable amount of black oxide film was present on the device, but after the deionized water washing, the black oxide film was completely removed.
FIG. 8 is a graph showing the relationship between the amount of current flowing through two metal electrodes according to a change in gate electrode after connecting positive and negative electrodes to two metal electrodes, connecting Si to Si below SiO 2 , Electrical properties. Specifically, Before (black) data before the deionized water washing showed a low current value for the voltage change due to the black oxide film, while (red) data after the deionized water washing increased the amount of current, And the characteristics were remarkably improved. [2] of FIG. 8 shows a result of re-measurement of the transistor device after being left for one day under a low humidity condition, and the device characteristics are decreased according to the black oxide film regeneration like before (black). However, it was confirmed that the electrical characteristics were restored again by performing the deionized water cleaning again.
Thus, it has been confirmed that the step of cleaning with water is a means for solving the sudden drop in the electrical characteristics of the electric device due to the black oxide film in various electric devices such as a transistor device including a black thin film or a black ultra thin film.
Control of thickness and uniform surface of black thin film is a key prerequisite for next generation materials. In the present invention, the black thin film was etched with active oxygen to a desired ultra-thin film thickness, the thickness of 3 nm or less was confirmed with Raman, and the photoluminescence property excellent in PL was confirmed. Also, by treating the black thin film with water to remove the black oxide thin film, the uniform surface of the black thin film was confirmed to improve the electric device characteristics.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Various modifications and variations are possible within the scope of the appended claims.
Claims (10)
Wherein the black thin film is formed by a method of mechanically peeling from a pure black pristine or a chemical vapor deposition method.
Wherein the active oxygen is generated through reaction of ultraviolet rays and oxygen in the chamber.
Having a thickness of 3 nm or less and having two PL peaks at a wavelength of 700 to 1000 nm.
Wherein the black ultra thin film has a single PL peak by a black atomic monolayers layer at a wavelength of 750 to 810 nm and a single PL peak by a black two atomic layer at a wavelength of 870 to 930 nm.
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| PCT/KR2016/002977 WO2016190531A1 (en) | 2015-05-28 | 2016-03-24 | Method for preparing black phosphorus thin film and black phosphorus thin film prepared thereby |
| US15/576,664 US10121658B2 (en) | 2015-05-28 | 2016-03-24 | Method of fabricating black phosphorus ultrathin film and black phosphorus ultrathin film thereof |
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