CN209929345U - Ferroelectric field regulated two-dimensional material PN junction photoelectric detector - Google Patents
Ferroelectric field regulated two-dimensional material PN junction photoelectric detector Download PDFInfo
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Abstract
The patent discloses a ferroelectric field regulated two-dimensional material PN junction photoelectric detector. The device structure comprises an insulating substrate, a bipolar two-dimensional semiconductor, a metal electrode and a ferroelectric functional layer from bottom to top in sequence. The preparation steps of the device are as follows: preparing a bipolar two-dimensional semiconductor on a substrate by using a mechanical stripping method, preparing a metal electrode by using an ultraviolet lithography or electron beam lithography method in combination with thermal evaporation and stripping processes, preparing a ferroelectric film on the structure by using a spin coating method, then enabling the polarization directions of ferroelectric materials on two sides above the two-dimensional material to be opposite by using a piezoelectric force microscope, regulating and controlling the two sides of the two-dimensional semiconductor to conduct electrons and holes respectively by using a ferroelectric local field to form an in-plane PN junction, and using the in-plane PN junction for photoelectric detection. When the device works, voltage is not required to be applied, photoelectric detection is realized by measuring current signal change under illumination, and the device can also be used for photovoltaic energy conversion. The detector has the characteristics of high sensitivity, low dark current, quick response, good stability, low power consumption and the like.
Description
Technical Field
The patent relates to a two-dimensional semiconductor photoelectric detector, in particular to a two-dimensional material PN junction photoelectric detector regulated and controlled by a ferroelectric field.
Background
Two-dimensional materials have received extensive attention and research in various fields in the past decade due to their unique properties. Two-dimensional materials represented by graphene, black phosphorus and molybdenum disulfide have great breakthroughs in different fields of biology, medicine, chemistry, physics and the like. Since most two-dimensional materials have semiconductor properties and their bandgaps are sufficiently different to cover the entire spectrum, they also show great potential in the field of photodetection. For example, the detection research of graphene in terahertz wave bands and the detection research of other two-dimensional materials on ultraviolet to infrared wave bands provide a new approach for the field of photoelectric detection.
Because two-dimensional materials are rich in types and various in energy band structures, and the surface does not have dangling bonds, various heterojunctions can be formed without the limitation of lattice matching. PN junctions are an important heterojunction as a fundamental component of modern electronic and optoelectronic devices and are widely used in diodes, bipolar transistors, light emitting diodes, solar cells, photodetectors, and the like. Conventional PN junction regions are typically formed by chemical doping, and many two-dimensional materials are inherently bipolar, such as WSe2,MoTe2Black phosphorus, etc., so that a PN junction can be formed in the same two-dimensional material by electrostatic doping, i.e., applying different voltages through the gate electrode to make a two-dimensional material in one pieceIs an electron or a hole, thereby forming an in-plane PN junction. Two gate electrodes close to each other are applied with different voltages, and the WSe is made by applying a negative voltage side2The Fermi level moves towards the top of a valence band so as to realize hole injection, and a positive voltage is applied to the other side so that the Fermi level moves towards the bottom of the valence band so as to realize electron injection, so that PN junctions are realized in the same two-dimensional material. The diode has good rectification characteristics, and the ideality factor and the rectification factor are respectively 1.9 and 105Has obvious light response to visible light, and the response rate reaches 210mA/W (Nature nanotechnology,2014,9(4): 262)]. In addition, the device has photovoltaic property and electroluminescent property, can be used for photovoltaic solar cells and light-emitting diodes, and has photoelectric conversion efficiency and luminous efficiency of 0.5% and 0.1%, respectively [ Nature nanotechnology,2014,9(4): 257]。
Despite the above advantages, the device requires the gate electrodes to be spaced apart very little (about three hundred nanometers), has extremely high process requirements, and requires two gate voltages to be applied continuously during operation, which greatly increases energy consumption. In order to overcome the defects, a method for regulating and controlling carrier types in the same two-dimensional material by using residual polarization of a ferroelectric material so as to form a PN junction is proposed. The ferroelectric material is a dielectric material with polarization characteristic, an external voltage is applied to polarize the ferroelectric material, and after the external voltage is removed, electric dipoles in the ferroelectric material are arranged in order, so that a huge built-in electric field can be generated. Therefore, the ferroelectric material is combined with the two-dimensional material, and the internal characteristics of the two-dimensional material are regulated and controlled by using a strong local electric field generated by the remnant polarization of the ferroelectric material. Applying a scanning voltage larger than the coercive field of the organic ferroelectric polymer polyvinylidene fluoride (P (VDF-TrFE)) through a needle point of a Piezoelectric Force Microscope (PFM), and ensuring that the voltage directions of the two ends are opposite to ensure that the P (VDF-TrFE) above the two-dimensional material is completely polarized and the ferroelectric domain directions are just opposite. Under the action of the ferroelectric material residual polarization field, holes and electrons are respectively injected into two sides of the bipolar two-dimensional material to form PN junctions, so that photoelectric detection is realized. Since the photocurrent of a single two-dimensional material is mainly due to the photoconductive effect, the photoresponse is slow and the responsivity is low. The photovoltaic characteristic of the PN junction formed under the regulation and control of the P (VDF-TrFE) polarization electric field can realize fast response and high response rate, and the voltage is not required to be applied all the time during working, so that the energy consumption is greatly reduced.
The device utilizes a strong local field generated by polarization of the ferroelectric material to regulate and control internal carriers of the two-dimensional material to form a PN junction, is applied to photoelectric detection, can effectively improve the performances of the two-dimensional material such as photoresponse rate, response time and the like, and does not need to apply additional grid voltage. The potential of the two-dimensional material on photoelectric detection is developed and utilized to a great extent, and the application pace of the two-dimensional material in the field of photoelectric detection is accelerated.
Disclosure of Invention
The patent provides a two-dimensional material PN junction photoelectric detector regulated and controlled by a ferroelectric field, and the application of the field of two-dimensional semiconductor photoelectric detection is widened.
The above patent utilizes ferroelectric material to regulate and control two-dimensional material to form in-plane PN junction, and is used for photoelectric detector. The detector structure utilizes a local electric field formed by ferroelectric polarization to enable one side of the bipolar two-dimensional material to be electrically conductive by electrons and the other side of the bipolar two-dimensional material to be electrically conductive by holes so as to form an in-plane PN junction, and can realize high sensitivity, low power consumption and rapid detection of devices.
The patent refers to a ferroelectric field regulated two-dimensional material PN junction photoelectric detector and a manufacturing method thereof, and is characterized in that the device structure is from bottom to top:
-a substrate 1 having a substrate orientation,
a two-dimensional semiconductor 2,
A metal electrode 3,
A ferroelectric functional layer 4,
Wherein the substrate 1 is a silicon substrate having a silicon dioxide layer;
wherein the two-dimensional semiconductor 2 is a bipolar transition metal compound with the thickness of 10-15 nanometers;
wherein the metal source electrode 3 is a chromium/gold electrode, the thickness of the chromium is 10 nanometers, and the thickness of the gold is 20 nanometers;
wherein the ferroelectric functional layer 4 is a polyvinylidene fluoride base ferroelectric polymer film;
the patent refers to a ferroelectric field regulated two-dimensional material PN junction photoelectric detector and its preparation method, characterized in that the device preparation includes the following steps:
1) substrate preparation
The substrate is a silicon substrate.
2) Preparation and transfer of bipolar transition metal compound two-dimensional semiconductor
And transferring the bipolar transition metal compound two-dimensional semiconductor to the substrate by adopting a mechanical stripping transfer method.
3) Electrode preparation
The metal electrode 3 is prepared by adopting an ultraviolet lithography or electron beam exposure technology and combining a thermal evaporation and lift-off process. The electrodes were chromium/gold with a thickness of 10/20 nm, respectively.
4) Preparation of polyvinylidene fluoride-based ferroelectric functional layer
And (3) preparing a polyvinylidene fluoride ferroelectric functional layer on the prepared device by using a spin coating method, and annealing at the temperature of 135 ℃ for 2 hours to ensure the crystallization characteristic of the functional layer.
5) Polarizing ferroelectric functional layers using piezoelectric force microscopy
The Piezoelectric Force Microscope (PFM) is a microscope that uses a conductive probe to detect the amount of electrostrictive deformation of a sample under an applied excitation voltage based on an Atomic Force Microscope (AFM), the probe of the PFM scans the sample in a contact mode, a voltage generated by a signal generator is applied between the PFM probe and a sample electrode, and a laser beam reflected by the back surface of a PFM microcantilever is used to monitor the amount of electrostrictive deformation. This patent uses the voltage applied to the sample by the tip of the PFM to polarize P (VDF-TrFE). After groping, the scanning voltage and the scanning frequency are respectively controlled to be +/-25V, and 1Hz is more suitable. In the scanning process, a scanning voltage of-25V is applied to the left side P (VDF-TrFE) of the material, a scanning voltage of +25V is applied to the right side, the polarization directions of the two sides are respectively far away from and point to the two-dimensional material, and then the ferroelectric field is utilized to regulate and control the two-dimensional material to form an in-plane PN junction which is used for a photoelectric detector.
When the device is operated, neither a gate voltage nor a voltage applied between the electrodes is required, and the schematic diagram of the operation state is shown in fig. 1. Under different wavelengths and radiation energy illumination, when the energy of incident photons is larger than the forbidden bandwidth of a two-dimensional material, the intrinsic absorption and the extrinsic absorption of the photons by a sample generate photon-generated carriers (electron-hole pairs). But only the minority carriers excited by intrinsic absorption can cause the photovoltaic effect. The photogenerated holes generated in the P area and the photogenerated electrons generated in the N area are majority electrons and are blocked by the potential barrier and cannot pass through the junction area. Only the photogenerated electrons in the P region and the photogenerated holes in the N region and the electron hole pairs (minority carriers) in the junction region can drift through the junction under the action of the built-in electric field when diffusing to the vicinity of the junction electric field. The photo-generated electrons are pulled to the N area, and the photo-generated holes are pulled to the P area, namely, the electron-hole pairs are separated by the built-in electric field. This results in photogenerated electron accumulation near the N-region boundary and photogenerated hole accumulation near the P-region boundary. They generate a photogenerated electric field in a direction opposite to the built-in electric field of the thermally balanced PN junction, which is directed from the P region to the N region. The potential barrier is lowered by the electric field, and the decrease is the photo-generated potential difference, the P terminal is positive, the N terminal is negative, and the Fermi level is separated at this time, so that the voltage drop is generated, as shown in FIG. 2. The photovoltaic effect is expressed in the current-voltage relationship, i.e. the curve moves down as a whole, generating open-circuit voltage and short-circuit current, as shown in fig. 3. The structure can be used for photoelectric detection and photovoltaic solar cells. Fig. 4 shows the actual test result (semi-logarithmic scale) of the device under 520nm wavelength illumination, and the device has obvious optical response, and the open-circuit voltage and the short-circuit current become larger as the incident light power increases.
The advantage of this patent lies in: the method is different from the traditional back gate field tube device that grid voltage needs to be added to adjust the Fermi level of the two-dimensional material so as to form electron or hole injection. And the space width of the ferroelectric domain is within 10 nanometers, so that the space size limitation of the gate electrode is eliminated. In addition, the realization of the two-dimensional semiconductor PN junction usually requires two materials to be overlapped together, the performance degradation of the device can be caused by the complicated process procedures such as transfer, photoresist removal and the like, and the PN junction can be realized on the same two-dimensional material by utilizing the ferroelectric material.
Drawings
Fig. 1 is a schematic cross-sectional view of an in-plane PN junction photodetector structure formed by ferroelectric material controlled two-dimensional material.
In the figure: 1 insulating substrate, 2 bipolar two-dimensional semiconductor, 3 metal electrode and 4 ferroelectric functional layer.
Fig. 2 is a schematic diagram of an energy band structure of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material during operation.
In the figure: efAt a Fermi level, EcTo the bottom of the tape guide EvIs the top of the valence band, qVbiBuilt-in potential difference, qV, for PN junctionocIs a photo-generated electromotive force.
Fig. 3 is a schematic view of a current-voltage relationship of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material under illumination.
In the figure: v and I are the voltage and current between the two electrodes, respectively. VocIs an open circuit voltage, IscIs a short circuit current.
Fig. 4 is a current-voltage relationship of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material in example 1 under illumination.
Fig. 5 is a current-voltage relationship of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material under illumination in example 2.
Fig. 6 is a current-voltage relationship of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material in example 3 under illumination.
Detailed Description
The following detailed description of embodiments of the present patent refers to the accompanying drawings in which:
the patent develops a two-dimensional semiconductor in-plane PN junction high-sensitivity photoelectric detector under the control of a ferroelectric local field. Through P (VDF-TrFE) ferroelectric polymer materials with opposite polarization directions on two sides, the bipolar two-dimensional semiconductor material conducts holes and electrons at the same time, and forms an in-plane PN junction for photoelectric detection, thereby realizing high response rate, high response speed and low power consumption.
The method comprises the following specific steps:
1. substrate selection
The substrate is a silicon/silicon dioxide substrate.
2. Two-dimensional semiconductor transfer fabrication
Bonding bipolar transition metal compound MoTe with adhesive tape2The crystal is mechanically stripped and then transferred to a substrate, MoTe2The thickness is 10-15 nanometers.
3. Electrode preparation
Preparing an electrode pattern by using an electron beam lithography method; preparing a metal electrode by utilizing a thermal evaporation technology, wherein the chromium is 10 nanometers, and the gold is 20 nanometers; the metal film was peeled off in combination with a lift-off method to obtain a metal electrode having a channel width of 5 μm.
4. Preparation of ferroelectric functional layer
Preparing a P (VDF-TrFE) ferroelectric functional layer by using a spin coating method, and annealing at the temperature of 135 ℃ for 2 hours to ensure the crystallization characteristic of the P (VDF-TrFE) ferroelectric functional layer.
5. Polarizing ferroelectric functional layers using piezoelectric force microscopy
The Piezoelectric Force Microscope (PFM) is a microscope which utilizes a conductive probe to detect the amount of electrostriction of a sample under an external excitation voltage on the basis of an Atomic Force Microscope (AFM), the probe of the PFM scans the sample in a contact mode, a voltage generated by a signal generator is applied between the PFM probe and a sample electrode, and a laser beam reflected by the back surface of a PFM micro-cantilever is utilized to monitor the amount of electrostriction of a ferroelectric material. P (VDF-TrFE) is polarized by the voltage applied to the sample by the PFM tip, and the scanning voltage and the scanning frequency are controlled to be +/-25V respectively, and 1Hz is suitable. In the scanning process, a scanning voltage of-25V is applied to the left side P (VDF-TrFE) of the material, a scanning voltage of +25V is applied to the right side, the polarization directions of the two sides are respectively far away from and point to the two-dimensional material, and then the ferroelectric field is utilized to regulate and control the two-dimensional material to form an in-plane PN junction. The photoelectric response characteristic under 520nm wavelength illumination is measured, and a remarkable photovoltaic effect is observed, as shown in fig. 4. The two-dimensional semiconductor photoelectric detector realizes high-sensitivity detection, fast response speed and low power consumption.
Example 1:
in this embodiment, a ferroelectric domain regulated MoTe is provided2An in-plane PN junction, the structural cross section of the device is shown in FIG. 1.
The detector comprises a substrate 1, a two-dimensional semiconductor 2, a metal electrode 3 and a ferroelectric functional layer 4 from bottom to top in sequence.
In embodiment 1, the substrate 1 is a silicon/silicon dioxide substrate, and the thickness of silicon dioxide is 285 nm; the two-dimensional semiconductor 2 is a two-dimensional material MoTe2A thickness of 10 nm; the metal electrode 3 is a chromium/gold electrode, 10 nanometers of chromium and 20 nanometers of gold; the ferroelectric functional layer 4 is a ferroelectric polymer P (VDF-TrFE) having a thickness of 50 nm.
Fig. 4 shows the current-voltage relationship under illumination of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material, where the photocurrent is significant at zero bias, the open-circuit voltage is 0.12 v, and the short-circuit current is 12 pa.
Example 2:
in this embodiment, a ferroelectric domain regulated MoTe is provided2An in-plane PN junction, the structural cross section of the device is shown in FIG. 1.
The detector comprises a substrate 1, a two-dimensional semiconductor 2, a metal electrode 3 and a ferroelectric functional layer 4 from bottom to top in sequence.
In embodiment 2, the substrate 1 is a silicon/silicon dioxide substrate, and the thickness of silicon dioxide is 285 nm; the two-dimensional semiconductor 2 is a two-dimensional material MoTe2A thickness of 12 nm; the metal electrode 3 is a chromium/gold electrode, 10 nanometers of chromium and 20 nanometers of gold; the ferroelectric functional layer 4 is a ferroelectric polymer P (VDF-TrFE) having a thickness of 50 nm.
Fig. 5 shows the current-voltage relationship under illumination of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material, where the photocurrent is significant at zero bias, the open-circuit voltage is 0.14 v, and the short-circuit current is 24 pa.
Example 3:
in this embodiment, a ferroelectric domain regulated MoTe is provided2In-plane PN junction, structure section of said deviceAs shown in fig. 1.
The detector comprises a substrate 1, a two-dimensional semiconductor 2, a metal electrode 3 and a ferroelectric functional layer 4 from bottom to top in sequence.
In embodiment 3, the substrate 1 is a silicon/silicon dioxide substrate, and the thickness of silicon dioxide is 285 nm; the two-dimensional semiconductor 2 is a two-dimensional material MoTe2A thickness of 15 nm; the metal electrode 3 is a chromium/gold electrode, 10 nanometers of chromium and 20 nanometers of gold; the ferroelectric functional layer 4 is a ferroelectric polymer P (VDF-TrFE) having a thickness of 50 nm.
Fig. 6 shows the current-voltage relationship under illumination of an in-plane PN junction photodetector formed by a ferroelectric material controlled two-dimensional material, where the photocurrent is significant at zero bias, the open-circuit voltage is 0.16 v, and the short-circuit current is 37 pa.
The structure device can effectively reduce dark current, improve the signal-to-noise ratio of the device, obviously improve the response speed of the device and reduce power consumption. The potential of the two-dimensional material in photoelectric detection application is developed and utilized to a great extent, and the application pace of the two-dimensional material in the photoelectric detection field is accelerated.
Claims (1)
1. The utility model provides a two-dimensional material PN junction photoelectric detector of ferroelectric field regulation and control, includes insulating substrate (1), two-dimensional semiconductor (2), metal electrode (3), ferroelectric function layer (4), its characterized in that:
the structure of the photoelectric detector is as follows: from bottom to top: the device comprises an insulating substrate (1), a two-dimensional semiconductor (2), a metal electrode (3) and a ferroelectric functional layer (4); wherein:
the substrate (1) is a silicon substrate with a silicon dioxide layer;
the two-dimensional semiconductor (2) is a bipolar transition metal compound, and the thickness of the two-dimensional semiconductor is 10-15 nanometers;
the metal electrode (3) is a chromium-gold composite electrode, the thickness of chromium is 10 nanometers, and the thickness of gold is 20 nanometers;
the ferroelectric function layer (4) is a polyvinylidene fluoride base ferroelectric polymer film.
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| CN113990979A (en) * | 2021-09-26 | 2022-01-28 | 北京工业大学 | Optical detection-optical storage integrated device |
| CN114122181A (en) * | 2021-11-25 | 2022-03-01 | 中国科学院电工研究所 | Ferroelectric-semiconductor coupling photovoltaic device and preparation method thereof |
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| CN109950403B (en) * | 2019-03-29 | 2024-03-26 | 中国科学院上海技术物理研究所 | Ferroelectric field regulated two-dimensional material PN junction photoelectric detector and preparation method thereof |
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| CN109950403B (en) * | 2019-03-29 | 2024-03-26 | 中国科学院上海技术物理研究所 | Ferroelectric field regulated two-dimensional material PN junction photoelectric detector and preparation method thereof |
| CN113990979A (en) * | 2021-09-26 | 2022-01-28 | 北京工业大学 | Optical detection-optical storage integrated device |
| CN113948594A (en) * | 2021-10-13 | 2022-01-18 | 北京理工大学 | Programmable photoelectric detector and preparation method thereof |
| CN114122181A (en) * | 2021-11-25 | 2022-03-01 | 中国科学院电工研究所 | Ferroelectric-semiconductor coupling photovoltaic device and preparation method thereof |
| CN114497287A (en) * | 2022-04-15 | 2022-05-13 | 浙江爱旭太阳能科技有限公司 | Solar cell composite assembly, preparation method thereof and photovoltaic system |
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