CN209434213U - A kind of thin layer of transparent ultraviolet photoelectron device - Google Patents

Abstract

The utility model provides a kind of thin layer of transparent ultraviolet photoelectron device, comprising: single conductance layer, the potential barrier insulating layer being arranged on single conductance layer, the transparent electrode layer being arranged on potential barrier insulating layer and the metal electrode being electrically connected with single conductance layer of substrate, setting on substrate；There is the window for exposing single conductance layer, the metal electrode is electrically connected by the window with single conductance layer formation, and the list conductance layer is the wide bandgap semiconductor layer of N-shaped or p-type doping on the potential barrier insulating layer.Ultraviolet double-side may be implemented in above-mentioned opto-electronic device, and has good optical detection performance, helps to improve luminescent properties and optical detection performance, and the manufacture craft for reducing complexity reduces cost.

Description

A kind of thin layer of transparent ultraviolet photoelectron device

Technical field

The utility model relates to a kind of thin layer of transparent ultraviolet photoelectron devices.

Background technique

Since Thomas Alva Edison et al. utility model osram lamp, the life style of the mankind are overturned the heavens Cover the variation on ground." as the sun rises, resting together with sunset " is no longer a kind of life style.Electroluminescent device it is practical The novel development for directly accelerating technological progress and civilization.After that, scientists constantly look for having more energy saving and real The new light sources of border application.1961, Robert Biard and Gary Pittman had found the infra-red radiation and second year of GaAs First visible light emitting diode of Nick Holonyak utility model.Recently, Nakamura Sh ū ji et al. utility model Brightness blue light LED simultaneously obtains Nobel Prize in physics.Light emitting diode (LED) is this can be by light together with being electrically coupled The development of device is increasingly mature, and compared with conventional light source, LED has small in size, and luminous efficiency is ideal, and the service life is long, switch time Fastly, the advantages that conducting voltage is relatively low, and mercury environmental pollution is small；LED is applied not only to illuminate, be also used for optic communication even industry and The fields such as medical treatment.General high-brightness LED manufacturing process is considerably complicated, includes more than ten a manufacturing steps, when this needs a large amount of Between and the cost of raw material.

Deep ultraviolet LED is still one of the goal in research field that scientist continues research in recent years, because they have extensively General application value, including biomedicine, environmental protection and public health etc.；But compared to other LED, the system of deep ultraviolet LED It makes in the presence of more challenges.This be primarily due to the ignorance to the powder injection molding of crystalline substrates and III-V nitride-based semiconductor with And technical obstacle, these challenges not only increase the difficulty of manufacture, also add cost of manufacture.

Therefore, it is necessary to manufacture a kind of new deep ultraviolet LED structure, to meet various competition features, including the fast of batch production Fast manufacturing process, it is inexpensive and multi-functional.Firstly, being exactly to find a kind of structure to replace p-n junction, because excessive p, n are adulterated Process may be along with the destruction of lattice structure；In addition, many semiconductors inherently are difficult to obtain p-type and n-type doping, this So that p-n junction is manufactured as challenge.

Utility model content

Technical problem underlying to be solved in the utility model is to provide a kind of thin layer of transparent ultraviolet photoelectron device, realizes The ultraviolet double-side of device, and there is good optical detection performance, luminescent properties and optical detection performance are helped to improve, and subtract Few complicated manufacture craft reduces cost.

In order to solve the above technical problems, the utility model provides a kind of thin layer of transparent ultraviolet photoelectron device, packet Include: substrate, the potential barrier insulating layer being arranged on single conductance layer, is arranged in potential barrier insulating layer setting single conductance layer on substrate On transparent electrode layer and the metal electrode that is electrically connected with single conductance layer；

There is the window for exposing single conductance layer, the metal electrode passes through the window and single electricity on the potential barrier insulating layer Conducting shell forms electrical connection, and the list conductance layer is the wide bandgap semiconductor layer of N-shaped or p-type doping.

In a preferred embodiment: the metal electrode is Ohmic contact with single conductance layer.

In a preferred embodiment: the opto-electronic device is optical detector.

The technical program compared with the background art, it has the following advantages:

1. the utility model uses a kind of " metal (Metal)-insulator (Insulator)-semiconductor (Semiconductor) " structure replaces p-n junction, and excessive p, n is avoided to adulterate the destruction of the adjoint lattice structure of process, And solve the problems, such as that many semiconductors inherently are difficult to obtain p-type and n-type doping；

2. the utility model avoids complicated manufacture craft, and reduce lacking of generating in prolonged deposition process It falls into, reduces the production cost simultaneously；

3. the ultraviolet double-side of device may be implemented in the utility model, and luminous efficiency is high, and luminescence band reaches ultraviolet light Wave band；

4. the utility model has good optical detection performance, a kind of optical detector can be obtained with this, there is fast light Response time and high responsiveness.

Detailed description of the invention

Fig. 1 shows the structural schematic diagram of the thin layer of transparent ultraviolet photoelectron device of the utility model embodiment；

Fig. 2 shows the signals of the manufacturing method process of the thin layer of transparent ultraviolet photoelectron device of the utility model embodiment Figure；

Fig. 3 shows the structural schematic diagram of single conductance layer of the utility model embodiment；

Fig. 4 shows luminescence generated by light (PL) spectrum of the utility model embodiment；

Fig. 5 has shown the insulating layer h-BN film SEM characterization and insulating properties test of the utility model embodiment；

Fig. 6 shows the SEM characterization and transmissivity test of the transparent electrode layer Cu nano wire of the utility model embodiment；

Fig. 7 shows the Ohmic contact test of the metal electrode of the utility model embodiment；

Fig. 8 shows the I-V curve of the rectification characteristic of the thin layer of transparent ultraviolet photoelectron device of the utility model embodiment；

Fig. 9 shows electroluminescent (EL) spectrum of the thin layer of transparent ultraviolet photoelectron device of the utility model embodiment；

Figure 10 shows the optical detection of the transient response of the thin layer of transparent ultraviolet photoelectron device of the utility model embodiment Performance.

Specific embodiment

Hereafter the utility model is described further by the drawings and specific embodiments.

With reference to Fig. 1-2, a kind of manufacturing method of thin layer of transparent ultraviolet photoelectron device is present embodiments provided, including as follows Step:

1. the preparation of single conductance layer n-AlGaN, the list conductance layer is the wide bandgap semiconductor layer of N-shaped or p-type doping.

1) it is prepared using Metallo-Organic Chemical Vapor deposition (MOCVD) method: not being mixed including 600nm on a sapphire substrate Miscellaneous Al_0.3Ga_0.7N buffer layer and 100nm Al_0.4Ga_0.6N；

2) Al adulterated using 1.5 μm of molecular beam epitaxial growth of N-shaped Si_0.3Ga_0.7N thin film, as shown in Figure 3, Figure 4；

3) n-AlGaN active layer is rinsed with ultrasonic impact in ethyl alcohol and DI water, cleans surface completely, finally utilizes Nitrogen gun removes surface water droplet and dust.

2. the preparation of potential barrier insulating layer h-BN:

1) it is prepared on Cu substrate using low-pressure chemical vapor deposition (LPCVD) method；

2) big quartz ampoule is set as reaction cavity, for providing vacuum environment and whole cavity gaseous environment and occurring to sink Product reaction；Big quartz pipe end is connected with vacuum pump by flange, including mechanical pump and molecular pump two-stage vacuum device, sealing Cavity can be evacuated to required vacuum degree after good, it is ensured that reaction is protected from airborne pollution, while by the exhaust gas generated in reaction process and By-product takes cavity out of.

3) setting tubule constitutes independent ventilation pipeline, is directly connected with independent gas circuit, and length is by BN predecessor warm area, out Mouth setting and reaction chamber section start.

4) there is mass flow controller to connect gas cylinder inside and outside outside pipeline, gas mass flow can be made using software accurate Control, and do the mixed gas supply of multiple gases.

5) predecessor of Borazane (ammonia borane) as B, N is chosen, after weighing 0.0120g, is placed in a small-sized quartz In boat and the center for being located at the first warm area is pushed it in tubule；Cu foil substrate is placed in the center of third warm area.

6) it sets temperature control panel and ventilation and starts to warm up program, when reaction temperature-raising region temperature raising is to 800-1000 DEG C, Outer tube passes to a certain proportion of hydrogen and argon gas mixed gas (10sccm H2 and 20sccm Ar), makes annealing treatment to substrate About 20-60 minutes, to remove substrate surface oxide layer and other absorption pollutants, increase the domain of Cu close with big reduction nucleation Degree, is conducive to the growth of high-quality thin film.

7) after the completion of annealing, reaction chamber temperature is promoted to 1050-1060 DEG C, meanwhile, warm area locating for predecessor is promoted to pre- If temperature (85-100 DEG C, 700~800 DEG C), starts growth phase at this time: being changed to be passed through 8sccm H from inner tube₂And 20sccm Ar conveys Borazane (gas flow and ratio can need to be scaled according to doping concentration and reaction speed).

8) heating schedule is automatically closed after reaction, and changes and continue to be passed through 5sccm H in outer tube₂It is used with 20sccm Ar Make protective gas, finally after naturally cooling to room temperature, close vacuum pump, opens after cavity restores vacuum degree and take out sample differentiation Front and back sides are placed in drying box stand-by.

3. potential barrier insulating layer h-BN film is transferred to single conductance layer；1) PMMA (polymethyl methacrylate) conduct is used The transfer method of medium.

2) boron nitride is protected in hexagonal boron nitride one layer of PMMA laid on, prepares a certain concentration ammonium persulfate ((NH₄)₂S₂O₈) solution, growth substrate copper sheet is removed, obtains the hexagonal boron nitride film floating of PMMA covering on etching solution.

3) it is transferred on single conductance layer n-AlGaN after rinsing in deionized water, the hexagonal boron nitride of PMMA covering is thin There are the windows for placing metal electrode on film, and part list conductance layer n-AlGaN is exposed.Then it is heating and curing, makes The hexagonal boron nitride film of PMMA covering is sufficiently contacted with single conductance layer n-AlGaN, and sample is placed in acetone soln Except PMMA.

4) it is finally annealed and further removes remaining PMMA.

4. the preparation of Ohmic electrode Ti/Al/Ti/Au:

1) Cu nano line electrode mask is made with aluminium-foil paper, and be wrapped on h-BN/n-AlGaN, pay attention to making electrode position It is corresponding with the window.

2) Ti (40nm)/Al (120nm)/Ti (40nm)/Au (80nm) metal electricity is sputtered using magnetron sputtering method respectively Pole.

3) reach Ohmic contact after short annealing 30s at 950 DEG C.

5. the preparation of transparent electrode Cu nano wire:

1) pre-reaction material of the 0.8mmol Copper dichloride dihydrate (CuCl22H2O) as copper atom is weighed (Precursor)；0.4mmol nickel acetylacetonate-Ni (acac) 2 is used as reducing agent；10ml oleyl amine is measured as reducing agent, dispersion Agent and structure directing agent (protective agent), three is mixed in three-necked flask.

2) three-necked flask is placed in constant-temperature heating magnetic stirring apparatus and carries out heating reaction, heating dress is adjusted by setting It sets, the accurate control to reaction temperature and reaction rate may be implemented.To avoid in reaction process Cu nano wire at high temperature It is oxidized, needs constantly to be passed through 50sccm high pure nitrogen (or argon gas) into container as protection gas.

3) when unit temp is increased to 80 DEG C, heated at constant temperature 20min.

4) by reaction unit continuous heating to 185 DEG C, 4 hours of heated at constant temperature.

5) after reaction, stop heating, after reaction solution is cooled to room temperature, Cu is centrifugated out from reaction product Nano wire, and be sealed in hexane solution.

6. transparent electrode Cu nano wire is transferred to insulating layer h-BN:

1) Cu nano wire transparent metal electrode is prepared using vacuum filtration stamping technique.

2) Cu nano line electrode mask is made with aluminium-foil paper, and be wrapped on h-BN/n-AlGaN, pay attention to making transparent electrode Part is located at the position for having h-BN to cover.

3) a certain amount of Cu nano wire-n-hexane ink is taken out, is diluted to a certain proportion of hexane solution certain dense (thickness that the amount by changing addition n-hexane can regulate and control transparent electrode influences the ginseng such as its transmissivity and square resistance to degree Number) and ultrasound, oscillation so that it is uniformly dispersed several minutes.

4) the Cu nano wire ink diluted is poured into the container of Suction filtration device, open vacuum mechanical pump take out just oneself Alkane, being formed on filter membrane has certain thickness equally distributed Cu nano wire film.

5) it takes the filter membrane for being covered with uniform Cu nano wire film off from suction filtration head with tweezers, makes to be covered with Cu nano wire It is fitted closely together with target substrate on one side.

6) apply certain pressure and uniformly rolling transfer at the filter membrane back side using boat-shaped seal, under the action of compression, Cu nano wire film comes into full contact with target substrate surface, and enables Cu nano wire so complete that be transferred in target substrate.

7) it is taken out after short annealing 20min at 300-400 DEG C after removing mask, it is organic on nano wire to remove Object, while copper nano-wire grid electric conductivity and mechanical performance are improved, to obtain the metallic film conductive grid being evenly distributed.

As the simple replacement of the present embodiment, it is readily modified as preparing potential barrier insulating layer directly on single conductance layer n-AlGaN； The preparation sequence of otherwise see-through electrode and metal electrode can overturn, i.e., first production transparent electrode prepares metal electrode again.

Thin layer of transparent ultraviolet photoelectron device has been obtained by the above method, comprising: the single electricity of substrate, setting on substrate Conducting shell, the potential barrier insulating layer being arranged on single conductance layer, the transparent electrode layer being arranged on potential barrier insulating layer and with the list The metal electrode of conductance layer electrical connection；

There is the window for exposing single conductance layer, the metal electrode passes through the window and single electricity on the potential barrier insulating layer Conducting shell forms electrical connection, and the list conductance layer is the wide bandgap semiconductor layer of N-shaped or p-type doping, and the transparent electrode layer is to receive The conductive, transparent two-dimensional material of rice noodles or atom level thickness.

For the feasibility and beneficial effect for verifying this programme, to the thin layer of transparent ultraviolet photoelectron device of this programme production into Row test and analysis:

1) the photoelectric properties test of single conductance layer n-AlGaN；

For the quality for studying n-AlGaN, measure room temperature PL spectrum: under 248nm laser excitation, front receives light and exists for discovery There are glow peaks at 282nm and 325nm, and through preliminary analysis, 324nm, which shines, is not as the impurity energy level of Si, because Si exists Ionization energy only has 0.2eV in AlGaN, but the transition between the acceptor level from Si impurity energy level to certain defects, be with The related nearly band-edge emission of defect；And luminous at 282nm then equally will not be from defect luminescence, because defect luminescence must It is generated in longer position, but it is ensured that photoluminescence wavelength has reached ultraviolet band, if attempting optimization n-AlGaN Structure or component, then be expected to step into deep ultraviolet band.

2) pattern of potential barrier insulating layer h-BN film and insulating properties test:

From fig. 5, it can be seen that there are some folds (Wrinkles) and the h-BN of single triangle for h-BN film Domain, fold are due to a complete h-BN film of engagement, its coefficient of expansion and the coefficient of expansion of copper foil are different institutes It causes, it can be determined that the integrality of h-BN film.

Test for insulating properties, we are illustrated using the measurement of I-V curve: it can be seen that under the voltage of 5V, The even h-BN film being covered on n-AlGaN shows the characteristic of insulation, equally illustrates that h-BN keeps good in transfer process Good integrality, while also explanation can use h-BN film as insulating layer, and the generation of leakage current can be prevented with this, can also be Free carrier is gathered in interface, to improve the luminous efficiency of opto-electronic device.

3) pattern of transparent electrode Cu nano wire and transmissivity test:

From fig. 6, it can be seen that the nano wire of preparation is uniformly dispersed, do not gather into bundles, impurity particle is few, nano wire purity It is high.In terms of nano wire pattern, diameter thickness is uniform, and diameter is averagely in 30nm hereinafter, have superelevation draw ratio (> 1600), explanation The Cu nano wire prepared has better quality, compared with the Cu nano wire that other technologies obtain in current report, we The result is that most thin in the world, draw ratio highest, surface be the most smooth, the highest nano wire of quality.

The photoelectric characteristic of transparent electrode material be measure whether the most important index with practical application value, it is general and Speech, it is intended that the higher the better for the transmissivity (T, optical properties) of transparent electrode, and the lower sheet resistance (Rs electrical properties) the better.I Cu nano wire is transferred on the quartz glass of high light transmittance, test its transmissivity using ultraviolet-visible photometer, can be with Find out that Cu nano wire has very high transmissivity in a very wide wavelength band (ultraviolet-infrared): sheet resistance Rs is 23 Ω/sq When, transmissivity T is up to 86.6%；And it is worth noting that, we can prepare different thickness by changing the concentration of nano wire The transparent electrode thin film of degree, Cu nano wire concentration is higher, and film is thicker, and transparent electrode electric conductivity is better, and transmissivity is then lower.

4) the Ohmic contact test of metal electrode:

By measuring the n-AlGaN after having sputtered Ti (40nm)/Al (120nm)/Ti (40nm)/Au (80nm) metal electrode The I-V curve of device, such as Fig. 7, discovery can achieve good Ohmic contact, and this Ohmic contact will not make inside semiconductor Equilibrium carrier concentration occur significant changes, nor affect on the I-E characteristic of device, hence it is demonstrated that selected metal electrode compared with It is suitable.

5) the I-V measurement of opto-electronic device:

In order to confirm the reason of tunneling mechanism is carrier transport in the device, we measure the I- from -10V to+10V V curve, such as Fig. 8, finding the device, there are apparent rectification characteristics, and electric current reaches greatly tens mA very much；In addition, binding isotherm Knowledge can find that direct tunnelling process is the leading mechanism of carrier transport in our devices.

6) electroluminescent (EL) spectral measurement of opto-electronic device:

For the luminous efficiency for measuring the device, the electroluminescent light of our the different tunnelling currents under room temperature forward bias Spectrum, such as Fig. 9 a, it can be seen from the figure that light emitting near 328nm belongs to nearly band edge hair under medium Injection Current It penetrates, and with the increase of tunnelling current, luminous intensity also occurs significantly increasing phenomenon.Due to the presence of h-BN insulating layer sum, It generates electric field and results in the accumulation of electronics；Tunneled holes in n-AlGaN Thin film conductive band are combined rapidly with electronics, 328nm nearby generates ultraviolet radioactive.The monopolizing characteristic that we realize is double-side, it is from Cu nanometers of high transparency Line electrode and Sapphire Substrate.EL spectrum in figure to be received from positive and negative.The luminous efficiency measured from the negative is positive 53%.

7) test of the optical detection performance of opto-electronic device:

Structural similarity based on light emitting diode and photodetector, the device of the utility model, which can be shown, passes through light Lie prostrate the light detection that effect generates.When being excited with 325nm laser (0.75mw/mm2), discovery detector has transient response, dark electricity Stream and photoelectric current are with good stability and repeated.Compared with other structures such as MSM and p-i-n photodetector, we The dark current measured is much smaller；Response time is fast~90ms and responsiveness up to 0.133A/W, such as Figure 10, illustrate that this is practical Novel device keeps excellent in responsiveness, therefore has good ultraviolet detection performance.

Skilled person will appreciate that when the technical parameter of the utility model changes in the following range, it is contemplated that Obtain same as the previously described embodiments or similar technical effect:

The potential barrier insulating layer is SiO₂, AlN and two dimension h-BN, MoS₂、MoSe₂、WS₂, silene, germanium alkene or black phosphorus etc. One of two-dimensional material is a variety of.

The transparent electrode layer is that the atom levels such as Ag nano wire, Cu nano wire, alloy nano-wire or graphene are thick conductive saturating One of bright two-dimensional material is a variety of.

The above is only the preferred embodiments of the utility model, but the scope of the utility model is without being limited thereto, the skill of this field Art personnel are easily envisaged that variation disclosed in the utility model or technical scope.Alternative solution is intended to cover practical at this In novel range.Therefore, the protection scope of the utility model should be determined by the scope of the claims.

Claims (3)

1. a kind of thin layer of transparent ultraviolet photoelectron device, characterized by comprising: substrate, setting single conductance layer on substrate, The potential barrier insulating layer that is arranged on single conductance layer, the transparent electrode layer being arranged on potential barrier insulating layer and with single conductance The metal electrode of layer electrical connection；

There is the window for exposing single conductance layer, the metal electrode passes through the window and single conductance layer on the potential barrier insulating layer Electrical connection is formed, the list conductance layer is the wide bandgap semiconductor layer of N-shaped or p-type doping.

2. a kind of thin layer of transparent ultraviolet photoelectron device according to claim 1, it is characterised in that: the metal electrode with The list conductance layer is Ohmic contact.

3. a kind of thin layer of transparent ultraviolet photoelectron device according to claim 1, it is characterised in that: the opto-electronic device For optical detector.