CN102130229B - Method for improving electroluminescent performance of n-ZnO/AlN/p-GaN heterojunction light-emitting diode - Google Patents
Method for improving electroluminescent performance of n-ZnO/AlN/p-GaN heterojunction light-emitting diode Download PDFInfo
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- CN102130229B CN102130229B CN2010106074138A CN201010607413A CN102130229B CN 102130229 B CN102130229 B CN 102130229B CN 2010106074138 A CN2010106074138 A CN 2010106074138A CN 201010607413 A CN201010607413 A CN 201010607413A CN 102130229 B CN102130229 B CN 102130229B
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Abstract
The invention discloses a method for improving the electroluminescent performance of an n-ZnO/AlN/p-GaN heterojunction light-emitting diode, the way of performing hydrogen plasma processing on the n-ZnO/AlN/p-GaN heterojunction light-emitting diode is adopted in the method for improving the electroluminescent performance of the n-ZnO/AlN/p-GaN heterojunction light-emitting diode, and the method specifically comprises the following steps: using a mask to cover the n-ZnO/AlN/p-GaN heterojunction light-emitting diode and exposing a ZnO part which needs to perform the hydrogen plasma processing; and sending the n-ZnO/AlN/p-GaN heterojunction light-emitting diode into a capacitance coupling plasma system for performing the hydrogen plasma processing, wherein is T, the radio frequency power is WH, and the processing time is tH. According to the invention, the electroluminescent performance of the n-ZnO/AlN/p-GaN heterojunction light-emitting diode can be improved.
Description
Technical field
The present invention relates to the semiconductor photoelectronic device technical field, particularly a kind of method of improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties.
Background technology
Light-emitting diode (LEDs) is considered to the third generation semiconductor lighting device after incandescent lamp, fluorescent lamp, and the advantage of its efficient and long life has caused people's research enthusiasm greatly.The light-emitting diode of main flow is to be processed by MOCVD extension GaN/InGaN SQW at present.Although GaN base LEDs has obtained development rapidly; Device still is faced with very big technical bottleneck aspect growth technique; High always like the defect density in the material; The substrate thermal diffusivity has much room for improvement, and device cost is too high, and there is " Droop " effect of external quantum efficiency reduction in device under big injection current condition.
ZnO is the third generation semi-conducting material after silicon, germanium and GaAs, is a kind of important II-VI family broad stopband direct band gap material.ZnO has identical crystal structure and less lattice mismatch with GaN, but the bigger energy gap of ZnO (～3.37eV) with high exciton bind energy (～60meV) make it be expected to replace the potential Material Used that GaN becomes the short-wave long light-emitting device.
In view of the above-mentioned advantage of ZnO, in recent years, zno-based LEDs had caused people's research enthusiasm greatly.And the preparation of the p type ZnO material of efficient stable is a difficult problem of scientific circles always, so the preparation of zno-based homojunction LEDs receives great restriction.Very maturation and the stable performance because the p type of GaN mixes, many people concentrate on the sight of research above the n-ZnO/p-GaN.Yet simple heterojunction is luminous very weak and defect luminescence is fairly obvious, then people expect in the middle of heterojunction, inserting the skim resistive formation, thereby charge carrier effectively is limited in the interface, improve the probability of radiation recombination.But barrier layer has increased the string resistance of device, reduces the cut-in voltage of device, is unfavorable for the raising of device overall performance.Thereby one of approach that addresses this problem is to improve the luminescent properties of the electric property raising device of ZnO film.
Summary of the invention
The technical problem that (one) will solve
Very big to current zno-based p-i-n light emitting diode string resistance, cut-in voltage is high, and the present situation that luminous efficiency is low, main purpose of the present invention are to provide a kind of method of the n-ZnO/AlN/p-GaN of improvement heterojunction light-emitting diode electroluminescent properties.
(2) technical scheme
For achieving the above object; The invention provides a kind of method of the n-ZnO/AlN/p-GaN of improvement heterojunction light-emitting diode electroluminescent properties; This method is to adopt n-ZnO/AlN/p-GaN heterojunction light-emitting diode is carried out the mode that hydrogen plasma is handled, and improves n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties.
In the such scheme, this method specifically comprises the steps: to use mask that n-ZnO/AlN/p-GaN heterojunction light-emitting diode is covered, and exposes and need carry out the ZnO part that hydrogen plasma is handled; N-ZnO/AlN/p-GaN heterojunction light-emitting diode sent into carry out hydrogen plasma in the capacitance coupling plasma system and handle; The temperature of device is T in the hydrogen plasma processing procedure, and radio-frequency power is W
H, the flow of hydrogen is F in the gas circuit, the pressure of hydrogen is P
H, the processing time is t
H
In the such scheme, before said hydrogen plasma was handled, the background vacuum of this capacitance coupling plasma system was pumped down to 1 * 10
-4Below the Pa.
In the such scheme, before said hydrogen plasma was handled, this capacitance coupling plasma system was passed into hydrogen, and it is 50-120sccm that the adjustment gas flowmeter makes the flow F of hydrogen in the gas circuit, adjustment gas pressure intensity P
HBe 50 to 200Pa.
In the such scheme, said hydrogen plasma treatment temperature T is a room temperature.
In the such scheme, said hydrogen plasma is handled radio-frequency power W
HBe 10 to 100W.
In the such scheme, said hydrogen plasma processing time t
HIt is 20 to 200 minutes.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, the present invention handles through one side of ZnO in the device being carried out hydrogen plasma; Electron concentration and mobility among the ZnO are greatly improved; And the AlN layer of high resistant can stop hydrogen atom in GaN, to spread, and makes hydrogen plasma handle back GaN layer and still keeps good electric property.
Find through experiment that 2, after the present invention carried out the hydrogen plasma processing to device, the string resistance of device reduced twice, cut-in voltage obviously reduces.Hydrogen plasma was handled after 80 minutes, and the electroluminescent properties of device is significantly improved, and under identical injection current, its room temperature electroluminescent intensity is three times before handling.
Description of drawings
Fig. 1 is the method flow diagram of the n-ZnO/AlN/p-GaN of improvement heterojunction light-emitting diode electroluminescent properties provided by the invention;
Fig. 2 is before the ZnO film hydrogen plasma processing of on Sapphire Substrate, growing and the Raman spectrum after handling;
Fig. 3 for before handling according to the n-ZnO/AlN/p-GaN heterojunction light-emitting diode hydrogen plasma of embodiment of the invention preparation with handle the different injection currents in back under room temperature electroluminescent compose; Wherein, a is the room temperature electroluminescent spectrum under the different injection currents before hydrogen plasma is handled, and b is that hydrogen plasma is handled the spectrum of the room temperature electroluminescent under the different injection currents after 80 minutes.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
The present invention adopts hydrogen plasma to handle n-ZnO/AlN/p-GaN heterojunction light-emitting diode; Can effectively improve the electroluminescent properties of zno-based LEDs; It is three times before handling that hydrogen is handled back luminous intensity of device under identical injection current; The series resistance of device reduces twice simultaneously, and cut-in voltage obviously descends.Therefore, the hydrogen plasma processing is a kind of simple but effective method that strengthens zno-based LEDs electroluminescent properties.
As shown in Figure 1; The method of improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties provided by the invention; Be to adopt n-ZnO/AlN/p-GaN heterojunction light-emitting diode is carried out the mode that hydrogen plasma is handled; Improve n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties, specifically comprise the steps:
Step 1: use mask that n-ZnO/AlN/p-GaN heterojunction light-emitting diode is covered, expose and to carry out the ZnO part that hydrogen plasma is handled;
Step 2: n-ZnO/AlN/p-GaN heterojunction light-emitting diode sent into carry out hydrogen plasma in the capacitance coupling plasma system and handle;
Step 3: the temperature of device is T in the hydrogen plasma processing procedure, and radio-frequency power is W
H, the flow of hydrogen is F in the gas circuit, the pressure of hydrogen is P
H, the processing time is t
H
Wherein, before hydrogen plasma was handled, the background vacuum of this capacitance coupling plasma system was pumped down to 1 * 10
-4Below the Pa; This capacitance coupling plasma system is passed into hydrogen, and the flow F of hydrogen is 50-120sccm, the pressure P of adjustment gas
HBe 50 to 200Pa.Hydrogen plasma treatment temperature T is a room temperature; Hydrogen plasma is handled radio-frequency power W
HBe 10 to 100W; Hydrogen plasma processing time t
HIt is 20 to 200 minutes.
Based on the method for improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties shown in Figure 1, the technical scheme that method adopted of the n-ZnO/AlN/p-GaN of improvement heterojunction light-emitting diode electroluminescent properties provided by the invention is:
1, utilize the MOCVD system at c-Al
2O
3The p-GaN film of growing high-quality on the substrate;
2, background vacuum in sample room is 3 * 10
-5Pa;
3, the equipment that uses during depositing Al N film is the rf magnetron sputtering system, and used target is the Al target, feeds Ar and N in the growth room
2Mist, gas ratio is 1: 1, gas pressure intensity is 1Pa, growth temperature is 700 ℃, growth time is 12 minutes;
Device therefor is the rf magnetron sputtering system when 4, depositing the n-ZnO film, and used target is that purity is 99.99% ZnO ceramic target, feeds Ar gas in the growth room, and pressure is 1Pa, and growth temperature is 600 ℃, and growth time is 60 minutes;
5, adopt wet etching, a side of the AlN film on the p-GaN film and ZnO film is eroded, expose the p-GaN film, the formation table top;
6, hydrogen plasma is handled and is adopted the capacitance coupling plasma etching system, and the background vacuum is evacuated to 1 * 10
-4Pa;
7, use mask that device is covered; Expose and need carry out the ZnO part that hydrogen plasma is handled, then device is sent in the capacitance coupling plasma etching system, keeping gas flow in the hydrogen plasma etching processing process is 80sccm; Gas pressure intensity is 180Pa; Etching temperature is a room temperature, and etching power is 80W, and etch period is 20 to 180 minutes.
8, preparation p type electrode on the table top of p-GaN film, the material of p type electrode is the NiAu alloy, manufacturing n type electrode on ZnO film, material therefor is the TiAu alloy.
The technical scheme that method adopted of improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties that provides based on the invention described above; Describe below in conjunction with a specific embodiment and to improve the electroluminescent method of n-ZnO/AlN/p-GaN heterojunction light-emitting diode, concrete preparation technology is following:
1, at c-Al
2O
3Deposition p-GaN film on the substrate, used growth apparatus is the MOCVD system, the hole concentration of p-GaN film is 10
16-10
18/ cm
3, hole mobility is 8-300cm
2/ Vs;
2, growing AIN film on the p-GaN film, used growth apparatus is the rf magnetron sputtering system, comprises Sample Room, settling chamber, vacuum system, radio-frequency power supply and matching system, substrate heating and temperature-controlling system, sample rotary system etc.;
3, the used working gas of growing AIN film is Ar and N
2Mist, the gas mixture ratio example is 1: 1, gas pressure intensity is 1.0Pa in the AlN thin film growth process, radio frequency sputtering power is 80W, underlayer temperature is 700 ℃, sputtering time is 12 minutes, growing period sample holder rotation makes film forming even;
4, growing ZnO thin-film on the AlN film, used growth apparatus is the rf magnetron sputtering system, the depositing temperature of ZnO film is 600 ℃; Working gas is Ar, and pressure is 1.0Pa, and growth power is 80W; Sedimentation time is 60 minutes, and the thickness of ZnO film is 300nm, and electron concentration is 10
17-10
18/ cm
3, electron mobility is 5-20cm
2/ Vs;
5, the hydrogen plasma etching adopts the capacitance coupling plasma etching system, and the background vacuum is evacuated to 1 * 10
-4Pa;
6, use mask that device is covered; Expose and need carry out the ZnO part that hydrogen plasma is handled, then device is sent in the capacitance coupling plasma etching system, keeping gas flow in the hydrogen plasma etching processing process is 80sccm; Gas pressure intensity is 180Pa; The device etching temperature is a room temperature, and etching power is 80W, and etch period is 20-180 minute;
7, adopt wet etching, a side of the ZnO film on the p-GaN film and AlN film is eroded, expose the p-GaN film, the formation table top;
8, on the table top of p-GaN film, make p type electrode, the material of p type electrode is the NiAu alloy, manufacturing n type electrode on ZnO film, and n type electrode is the TiAu alloy.
Test result and analysis
According to the process conditions that provide in the foregoing description, utilize the rf magnetron sputtering system on GaN (0001) substrate, to prepare n-ZnO/AlN/p-GaN heterojunction light-emitting diode.The adding of AlN layer greatly reduces the defect concentration in interface, has improved the heterojunction boundary quality.
Fig. 2 for the ZnO film of growing on the Sapphire Substrate before hydrogen plasma is handled with handle after Raman spectrum, before the hydrogen plasma processing, from curve, can find out four tangible Raman peaks, be positioned at 98,332,438,577cm
-1, four kinds of different phonon vibration patterns of the corresponding ZnO of difference.After hydrogen plasma is handled, occurred two vibration mode peaks relevant among the figure, laid respectively at 275 and 510cm with hydrogen
-1, show that hydrogen atom has entered into ZnO film.
Fig. 3 be before the device hydrogen plasma is handled with handle the different injection currents in back room temperature electroluminescent spectrum down, can find out that from a of Fig. 3 the device glow peak is positioned at 403nm, defect luminescence is by inhibition fully, along with the increase of injection current, luminous enhancing gradually.Hydrogen plasma is handled after 80 minutes the room temperature electroluminescent of device under different injection currents and is composed shown in the b of Fig. 3; Hydrogen is handled the electroluminescence under identical injection current of back device and is strengthened greatly; The glow peak peak position did not obviously move when injection current was 8mA, and luminous intensity is three times before hydrogen plasma is handled.On the one hand, the insertion of AlN layer has reduced the quantity of interface non-radiative recombination center, has improved the heterojunction boundary quality; On the other hand, hydrogen plasma is handled the raising help electron concentration and mobility among the ZnO, and high resistant AlN layer can stop the diffusion of hydrogen atom in the GaN layer simultaneously, the good electric property of maintenance GaN film.Therefore, the raising of device interfaces quality and the good electric property of ZnO layer were the reasons that the device electroluminescence strengthens after hydrogen plasma was handled.
Conventional zno-based LEDs is because interface quality is undesirable; There is more non-radiative recombination center at the interface; Cause the device luminous efficiency lower; Although in the middle of heterojunction, insert the luminescent properties that one deck barrier layer can improve device to a certain extent, the insertion of high resistant barrier layer has increased the series resistance of device greatly, has improved the cut-in voltage of device.The method that we adopt hydrogen plasma to handle; Make device electroluminescence intensity under identical injection current situation improve three times; Through adopting different processing times and hydrogen plasma to handle post growth annealing, we find that hydrogen has relative advantages of higher stability in device.The raising of electron concentration and mobility is the main cause that the device luminescent properties improves among interface quality that device is desirable and the hydrogen plasma processing back ZnO.This method is simply effective, and cost is lower, and it is obvious to strengthen illumination effect, is a kind of effective ways that improve zno-based LEDs luminescent properties.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. method of improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties; It is characterized in that; This method is to adopt n-ZnO/AlN/p-GaN heterojunction light-emitting diode is carried out the mode that hydrogen plasma is handled; Improve n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties, this method specifically comprises the steps:
Use mask that n-ZnO/AlN/p-GaN heterojunction light-emitting diode is covered, expose and to carry out the ZnO part that hydrogen plasma is handled; And
N-ZnO/AlN/p-GaN heterojunction light-emitting diode sent into carry out hydrogen plasma in the capacitance coupling plasma system and handle;
Wherein, the temperature T of device is a room temperature in the hydrogen plasma processing procedure, radio-frequency power W
HBe 10 to 100W, the flow F of hydrogen is 50-120sccm in the gas circuit, the pressure P of hydrogen
HBe 50 to 200Pa, processing time t
HIt is 20 to 200 minutes.
2. the method for improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties according to claim 1 is characterized in that, before said hydrogen plasma was handled, the background vacuum of this capacitance coupling plasma system was pumped down to 1 * 10
-4Below the Pa.
3. the method for improving n-ZnO/AlN/p-GaN heterojunction light-emitting diode electroluminescent properties according to claim 1 is characterized in that, before said hydrogen plasma was handled, this capacitance coupling plasma system was passed into hydrogen.
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