CN110611017A - Method for improving transparent conductivity and heat dissipation of LED by growing graphene on gallium nitride - Google Patents
Method for improving transparent conductivity and heat dissipation of LED by growing graphene on gallium nitride Download PDFInfo
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
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- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
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- 238000001035 drying Methods 0.000 claims description 4
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- 239000012535 impurity Substances 0.000 claims description 4
- 238000009616 inductively coupled plasma Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 229910001258 titanium gold Inorganic materials 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 claims description 3
- 238000001039 wet etching Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/64—Heat extraction or cooling elements
- H01L33/641—Heat extraction or cooling elements characterized by the materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0025—Processes relating to coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0066—Processes relating to semiconductor body packages relating to arrangements for conducting electric current to or from the semiconductor body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0075—Processes relating to semiconductor body packages relating to heat extraction or cooling elements
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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a method for improving the transparent conductivity and heat dissipation of an LED (light-emitting diode) by growing graphene on gallium nitride. And finally, a transparent conducting layer formed by the ultrathin platinum and the graphene is utilized to enhance the current expansion and heat dissipation of the surface of the LED. In the invention, the graphene is directly grown on the surface of the LED without transfer, the preparation efficiency of the device is greatly improved, and the process flow is greatly simplified. The invention is expected to promote the commercial application of the graphene transparent conductive film on the blue light LED substrate.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to direct growth of graphene and a method for improving the performance of a gallium nitride-based LED device by using the graphene directly grown on gallium nitride as a transparent conducting and heat dissipating layer.
Background
Gallium nitride (GaN), which is a representative nitride semiconductor material, has attracted considerable attention as an important material for light-emitting diodes (LEDs) of electronic devices, but it is difficult to form an ohmic contact electrode on p-GaN, and therefore, in order to effectively spread current and reduce a forward operating voltage without affecting front light emission, a transparent conductive layer needs to be added on p-GaN. Currently, in optoelectronic devices, the mainstream transparent electrode material is Indium Tin Oxide (ITO). However, the content of indium element in earth crust is very limited, and the cost is very high. Since 2004, graphene shows great application potential in the fields of nanoelectronics, energy, chemistry, biomedicine and the like due to its excellent properties such as high transparency, high conductivity, high mobility, high thermal conductivity, high mechanical strength and the like, and the transparency of graphene is reduced by only 2.3% from ultraviolet to near infrared, theoretically every layer is added. Therefore, graphene is likely to be a substitute for ITO.
The conventional process is to transfer the graphene grown on the metal substrate to a new substrate by a wet process, which is complex and tedious and often results in non-ideal interfaces between the graphene and the gallium nitride, such as metal residues, oxides, pores and wrinkles. At present, few people study the growth of graphene on platinum. While platinum has a greater catalytic ability for hydrocarbon decomposition and subsequent graphene formation than copper. In addition, platinum has a particularly large work function and is one of the best known metals in contact with gallium nitride, and therefore we use ultra-thin layers of platinum as a catalyst for the direct growth of graphene on GaN/sapphire substrates. The method avoids a series of problems in the transfer process, and has the advantages of higher repeatability and simpler process. Because the thickness of Pt is extremely thin, evaporation and agglomeration occur in the growth process, and the light emitting of the LED cannot be influenced. Meanwhile, the growth environment of plasma auxiliary enhancement and cold wall vertical chemical vapor deposition is utilized, so that the growth temperature is reduced, the interface of the nitrogenized graphene is protected, the growth is accelerated, the growth efficiency is improved, and the growth cost is reduced. In addition, by measuring the electrical, optical and thermal properties, we also find that the addition of the graphene not only improves the LED luminous current and reduces the starting voltage and luminous power consumption, but also has obvious advantages in heat dissipation, and has wide prospects in improvement of the reliability and durability of devices and prolonging of service life.
Disclosure of Invention
The invention has the effect of providing a method for improving the performance of a gallium nitride-based LED device by directly growing graphene on gallium nitride as a transparent conductive and heat dissipation layer.
The technical scheme adopted by the invention is a method for improving the transparent electric conduction and the heat dissipation of an LED by growing graphene on gallium nitride, the implementation process of the method is as follows,
step 1: taking an epitaxial structure diagram 1, wherein the epitaxial structure of the gallium nitride light-emitting diode chip comprises a sapphire substrate (1), a u-shaped gallium nitride layer (2), an n-shaped gallium nitride layer (3), an active layer (4) and a p-shaped gallium nitride layer (5), boiling and cleaning with acetone twice to remove organic impurities on the surface of the epitaxial structure of the gallium nitride light-emitting diode chip, boiling and cleaning with ethanol twice to remove acetone on the surface, washing with deionized water for 30 times to remove ethanol on the surface, and drying the surface of the epitaxial structure of the gallium nitride light-emitting diode chip with a nitrogen gun;
step 2: a thin layer of 2nm platinum (6) is sputtered on p-type gallium nitride (5) of a gallium nitride light-emitting diode chip epitaxial structure to serve as a catalyst, and graphene (7) of a transparent conducting layer directly grows.
And step 3: depositing a layer of metal film on the surface of the substrate on which the graphene grows, and corroding the metal film to form a pattern by utilizing a photoetching process. And finally, using the patterned metal film as a mask, carrying out dry etching on the substrate, and sequentially etching away the graphene (7), the platinum (6), the p-type gallium nitride (5) and the active layer (4) without the metal mask region, thereby finally exposing the n-type gallium nitride layer. The material of the metal mask region is common metal mask materials such as nickel, cobalt or nickel-copper alloy;
and 4, step 4: after the metal mask layer is corroded by a wet etching process, a p electrode and an n electrode are prepared on the surface of the substrate by utilizing the traditional photoetching-electrode deposition-stripping semiconductor process. The method for depositing the electrode is electron beam evaporation or magnetron sputtering. The p electrode and the n electrode are made of titanium gold electrodes or other common electrodes such as nickel gold and cadmium gold.
In step 2 of the present invention, the graphene growth system used was a cold wall vertical CVD model BLACK MAGIC manufactured by AIXTRON, as shown in fig. 4. The equipment mainly comprises an equipment main body, a vacuum pump set and a water cooling machine. Different from the traditional hot wall tube type CVD, the CVD is heated by an electric heating wire, the heating area is large, the heating and cooling time is long, and the energy consumption is high. Only the middle heating plate part (11) of the system is used for effective heating, the two stainless steel supporting columns are respectively a second supporting column (14) and a third supporting column (15), electricity is conducted between the second supporting column (14) and the third supporting column (15), and a sample is heated through joule heat. In the process, the cavity of the reaction chamber is cold, and the temperature of circulating water in the cavity is controlled to be maintained at 25 ℃ by a water cooling machine. The growth temperature can be reduced by the aid of the enhanced graphite plasma sheet (12) in the cavity, and the special growth mechanism of the device has the advantages of high temperature rising and cooling speed, high graphene growth speed and low energy consumption. The process manufacturing method has the characteristics of low temperature, short time, simple manufacturing method and the like. The temperature for growing the graphene on the metal platinum alone is generally over 1000 ℃, and the condition is only suitable for the graphene transfer process. High temperature easily causes interface damage to the light emission of the gallium nitride-based diode to a certain degree, and causes the problems of uneven light emission, poor brightness, poor conductivity and the like. The problems of graphene wrinkles, holes, ion residues and the like are easily caused in the transfer process, and the transfer method is multiple in steps and difficult to operate. In order to solve the problems, 2nm platinum is sputtered on a gallium nitride substrate to directly grow graphene to manufacture a device. The characteristic of the local heating of the cold wall vertical CVD is utilized to realize rapid temperature rise and fall and shorten the growth time. The direct current is utilized to start through the plasma graphite sheet to generate a plasma electric field with certain power, the auxiliary heating system provides energy for the decomposition of gas, the graphene is synthesized, and the graphene can be synthesized only by growing at the temperature of 600 ℃ for 20 minutes. The light emitting diode added with the graphene not only makes up the problem that the conductivity of the device is poor in the annealing process during growth, as shown in fig. 5, compared with the device without the graphene, the current is doubled under the same voltage, the voltage is turned on, the working voltage is lower, the heat dissipation is faster under the same working current, and the heat diffusion is more uniform.
Drawings
FIG. 1 is a schematic view of an epitaxial structure of a GaN LED chip according to the present invention;
FIG. 2 is a schematic structural diagram of a GaN LED chip of the invention after etching;
FIG. 3 is a schematic structural diagram of a GaN LED chip of the present invention after fabrication;
fig. 4 is a schematic structural diagram of the graphene direct growth apparatus of the present invention;
wherein: 9. gas is introduced into a shower head of the chamber, 10 the substrate, 11 the heating plate, 12 the plasma glow plate, 13 the first support column, 14 the second support column, 15 the third support column, 16 and the fourth support column.
Fig. 5 is a current characteristic curve of the final LED device of the present invention.
Detailed Description
The key point of the invention is that graphene is rapidly and directly grown on p-type gallium nitride at low temperature by using thin platinum as a catalyst, a series of problems of transfer in the traditional process are avoided, and the blue light LED device with high brightness, low power consumption and good heat dissipation is successfully prepared.
The invention provides a method for improving the performance of a gallium nitride-based LED device by directly growing graphene on gallium nitride as a transparent conducting and heat dissipating layer, which comprises the following steps:
step 1: taking an epitaxial structure diagram 1, wherein the epitaxial structure comprises a sapphire substrate (1), a u-shaped gallium nitride layer (2), an n-shaped gallium nitride layer (3), an active layer (4) and a p-shaped gallium nitride layer (5), boiling and cleaning with acetone twice to remove organic impurities on the surface, boiling and cleaning with ethanol twice to remove acetone on the surface, washing with deionized water 30 times to remove ethanol on the surface, and drying the surface with a nitrogen gun.
Step 2: a thin platinum layer (6) is sputtered on a p-type gallium nitride (5) of an epitaxial structure to serve as a catalyst to directly grow transparent conductive layer graphene (7), the growth time is shortened by utilizing a vertical cold wall chamber environment, and the growth temperature is reduced by plasma enhancement assistance.
And step 3: depositing a layer of metal film on the surface of the substrate on which the graphene grows, and corroding the metal film to form a pattern by utilizing a photoetching process. And finally, using the patterned metal film as a mask, carrying out dry etching on the substrate, and sequentially etching away the graphene (7), the platinum (6), the p-type gallium nitride (5) and the active layer (4) without the metal mask region, thereby finally exposing the n-type gallium nitride layer. The metal mask material in this step may be common metal mask materials such as nickel, cobalt, nickel-copper alloy, and the like.
And 4, step 4: after the metal mask layer is corroded by a wet etching process, a p electrode and an n electrode are prepared on the surface of the substrate by utilizing the traditional photoetching-electrode deposition-stripping semiconductor process. The method of depositing the electrode may be electron beam evaporation or magnetron sputtering. The electrode can be made of titanium gold electrode, or other common electrodes such as nickel gold, cadmium gold and the like.
Example (c);
referring to fig. 1 to 4, the present invention provides a method for improving the performance of a gan-based LED device by directly growing graphene on gan as a transparent conductive and heat dissipation layer, including:
step 1: taking an epitaxial structure diagram 1, wherein the epitaxial structure comprises a sapphire substrate (1), a u-type gallium nitride layer (2), an n-type gallium nitride layer (3), an active layer (4) and a p-type gallium nitride layer (5), boiling and cleaning with acetone twice to remove organic impurities on the surface, boiling and cleaning with ethanol twice to remove acetone on the surface, and washing with deionized water 30 times to remove ethanol on the surface. Drying the surface by a nitrogen gun;
step 2: sputtering a metal layer platinum with the thickness of 2 nm;
and step 3: by adopting a CVD method, graphene is directly grown on 2nm platinum, 40W direct current plasma enhancement assists in reducing the growth temperature, acetylene and argon are mixed at a ratio of 100:250sccm at 600 ℃, and the growth lasts 20 minutes. Obtaining a graphene film growing on the platinum;
and 4, step 4: depositing a metal mask layer of nickel with the thickness of 100nm, wherein the metal mask material in the step can also be common metal mask materials such as cobalt, nickel-copper alloy and the like;
and 5: corroding the metal film into a pattern by utilizing a photoetching process;
step 6: and washing off the photoresist, and etching away the graphene (7), the platinum (6), the p-type gallium nitride (5) and the active layer (4) without the metal mask region in sequence by adopting ICP (inductively coupled plasma) dry etching, so as to finally expose the n-type gallium nitride layer and form an n-type step. Removing the remaining metal mask by using corrosive liquid;
and 7: and manufacturing photoresist patterns on the surfaces of the graphene layer and the p-type gallium nitride layer by using a photoetching method, and manufacturing a metal layer by using an evaporation or sputtering method, wherein the metal layer is titanium gold, or other common electrodes such as nickel gold, cadmium gold and the like. The thicknesses of the metal layers were 15nm and 300nm, respectively, and the metal layers except the electrode positions were peeled off to form final metal electrodes of 260X 515. mu.m2A device.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modifications or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A method for improving the transparent conductivity and heat dissipation of an LED by growing graphene on gallium nitride is characterized by comprising the following steps: the method is implemented as follows,
step 1: taking an epitaxial structure diagram 1, wherein the epitaxial structure of the gallium nitride light-emitting diode chip comprises a sapphire substrate (1), a u-shaped gallium nitride layer (2), an n-shaped gallium nitride layer (3), an active layer (4) and a p-shaped gallium nitride layer (5), boiling and cleaning with acetone twice to remove organic impurities on the surface of the epitaxial structure of the gallium nitride light-emitting diode chip, boiling and cleaning with ethanol twice to remove acetone on the surface, washing with deionized water for 30 times to remove ethanol on the surface, and drying the surface of the epitaxial structure of the gallium nitride light-emitting diode chip with a nitrogen gun;
step 2: sputtering a thin layer of 2nm platinum (6) as a catalyst on p-type gallium nitride (5) of a gallium nitride light-emitting diode chip epitaxial structure to directly grow graphene (7) of a transparent conducting layer;
and step 3: depositing a layer of metal film on the surface of the substrate on which the graphene grows, and corroding the metal film to form a pattern by utilizing a photoetching process; finally, the patterned metal film is used as a mask, the substrate is subjected to dry etching, graphene (7), platinum (6), p-type gallium nitride (5) and an active layer (4) without the metal mask region are sequentially etched, and the n-type gallium nitride layer (3) is finally exposed;
and 4, step 4: after the metal mask layer is corroded by a wet etching process, a p electrode and an n electrode are prepared on the surface of the substrate by a photoetching-electrode deposition-stripping semiconductor process.
2. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: the method for depositing the electrode is electron beam evaporation or magnetron sputtering.
3. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: the p electrode and the n electrode are made of titanium gold electrodes, nickel gold electrodes or cadmium gold electrodes.
4. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: the material of the metal mask region is nickel, cobalt or nickel-copper alloy.
5. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: and etching the metal film to form a pattern by utilizing a photoetching process.
6. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: and performing dry etching by adopting ICP (inductively coupled plasma) to expose the n-type gallium nitride layer and form an n-type step.
7. The method of claim 1, wherein the graphene grown on the gallium nitride is used for improving the transparent electric conduction and the heat dissipation of the LED, and the method comprises the following steps: and (3) manufacturing photoresist patterns on the surfaces of the graphene layer and the p-type gallium nitride layer by using a photoetching method, manufacturing a metal layer by using an evaporation or sputtering method, and stripping the metal layer except the electrode position to form a final metal electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110611017B (en) | 2021-09-17 |
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