Abstract:
A method of forming a low temperature-grown buffer layer having the steps of: placing a Ga 2 O 3  substrate in a MOCVD apparatus; providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition having an atmosphere temperature of 350° C. to 550° C.; and supplying a source gas having two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate.

Description:
[0001]     The present application is based on Japanese patent application Nos. 2005-101603 and 2006-016988 filed on Mar. 31, 2005 and Jan. 25, 2006, respectively, the entire contents of which are incorporated herein by reference.  
       BACKGROUND OF THE INVENTION  
       [0002]     1. Field of the Invention  
         [0003]     This invention relates to a light emitting element made of a semiconductor material and a light emitting device using the light emitting element. Especially, this invention relates to a method of forming a low temperature-grown buffer layer that a Ga 2 O 3  substrate does not deteriorate even when forming the low temperature-grown buffer layer in a H 2  atmosphere, a method of making a light emitting element with GaN having an excellent crystalline quality by using the low temperature-grown buffer layer thus formed, the light emitting element, and a light emitting device using the light emitting element.  
         [0004]     2. Description of the Related Art  
         [0005]     GaN-based semiconductors are known as a material for light emitting element in blue or short-wavelength emission region. Especially, a light emitting element to emit ultraviolet light is estimated to be used for, e.g., a fluorescent lamp which is desired to be mercury-free in consideration of environment, a photocatalyst which provides a clean environment, a light source for a high-capacity recoding medium such as a DVD (digital versatile disk). The light emitting element is desired to have a further short-wavelength.  
         [0006]     GaN is very high in melting point and in nitrogen equilibrium vapor pressure. Therefore, it is difficult to make a bulk single-crystal GaN substrate with a high quality and large area. Thus, a GaN growth method has been used that a sapphire (Al 2 O 3 ) substrate is used as an underlying substrate, forming a buffer layer thereon to reduce the lattice mismatch with GaN, growing a GaN-based semiconductor thereon. However, a light emitting element using the GaN-based semiconductor has a limitation that its electrode structure is to be horizontally disposed. Further, it is desired that its lifetime and its handling easiness in mounting are further enhanced when it is applied to various uses.  
         [0007]     Under these circumstances, it is recently proposed to use as a substrate β-Ga 2 O 3 , a transparent material, which is capable of transmitting ultraviolet light and of being manufactured as a bulk single crystal (See, e.g., Japanese Journal of Applied Physics., Vol. 44, No. 1, 2005 pp. L7-L8, hereinafter referred to as related art 1).  
         [0008]     The related art 1 discloses a light emitting element that a low temperature-grown GaN buffer layer is formed on the β-Ga 2 O 3  substrate at 600° C., and GaN is grown thereon at 1070° C.  
         [0009]     However, the light emitting element of the related art 1 has a problem that β-Ga 2 O 3  may be thermally decomposed in the process of forming the low temperature-grown GaN buffer layer and therefore it is difficult to grow a high-quality GaN-based semiconductor layer thereon in a subsequent process.  
         [0010]     It is generally known that the GaN buffer layer is formed on the β-Ga 2 O 3  substrate in a H 2  atmosphere. It is exactly found by the inventors that the surface of the β-Ga 2 O 3  substrate deteriorates into black when the buffer layer is formed at a temperature higher than 600° C. in the H 2  atmosphere.  
       SUMMARY OF THE INVENTION  
       [0011]     It is an object of the invention to provide a method of forming a low temperature-grown buffer layer that a Ga 2 O 3  substrate does not deteriorate even when forming the low temperature-grown buffer layer in a H 2  atmosphere.  
         [0012]     It is a further object of the invention to provide a method of making a light emitting element with GaN having an excellent crystalline quality by using the low temperature-grown buffer layer thus formed, the light emitting element, and a light emitting device using the light emitting element.  
         [0000]     (1) According to one aspect of the invention, a method of forming a low temperature-grown buffer layer comprises the steps of:  
         [0013]     placing a Ga 2 O 3  substrate in a MOCVD apparatus;  
         [0014]     providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition comprising an atmosphere temperature of 350° C. to 550° C.; and  
         [0015]     supplying a source gas comprising two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate.  
         [0000]     (2) According to one aspect of the invention, a method of forming a low temperature-grown buffer layer comprises the steps of:  
         [0016]     acid-cleaning a Ga 2 O 3  substrate;  
         [0017]     placing the acid-cleaned Ga 2 O 3  substrate in a MOCVD apparatus;  
         [0018]     providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition comprising an atmosphere temperature of 350° C. to 550° C.; and  
         [0019]     supplying a source gas comprising two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate.  
         [0000]     (3) According to one aspect of the invention, a method of forming a low temperature-grown buffer layer comprises the steps of:  
         [0020]     nitriding a Ga 2 O 3  substrate;  
         [0021]     placing the nitrided Ga 2 O 3  substrate in a MOCVD apparatus;  
         [0022]     providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition comprising an atmosphere temperature of 350° C. to 550° C.; and  
         [0023]     supplying a source gas comprising two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate.  
         [0000]     (4) According to one aspect of the invention, a method of forming a low temperature-grown buffer layer comprises the steps of:  
         [0024]     acid-cleaning a Ga 2 O 3  substrate;  
         [0025]     nitriding the acid-cleaned Ga 2 O 3  substrate;  
         [0026]     placing the nitrided Ga 2 O 3  substrate in a MOCVD apparatus;  
         [0027]     providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition comprising an atmosphere temperature of 350° C. to 550° C.; and  
         [0028]     supplying a source gas comprising two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate.  
         [0029]     In the above invention (1)-(4), the following modifications and changes can be made.  
         [0030]     (i) The nitriding step is conducted in a temperature range of 750° C. to 850° C.  
         [0031]     (ii) The low temperature-grown buffer layer comprises Al x Ga 1-x N (0≦x≦1).  
         [0000]     (5) According to another aspect of the invention, a method of making a light emitting element comprises the steps of:  
         [0032]     acid-cleaning a Ga 2 O 3  substrate;  
         [0033]     nitriding the acid-cleaned Ga 2 O 3  substrate;  
         [0034]     placing the nitrided Ga 2 O 3  substrate in a MOCVD apparatus;  
         [0035]     providing a H 2  atmosphere in the MOCVD apparatus and setting a buffer layer growth condition comprising an atmosphere temperature of 350° C. to 550° C.;  
         [0036]     supplying a source gas comprising two or more of TMG, TMA and NH 3  onto the Ga 2 O 3  substrate in the buffer layer growth condition to form the low temperature-grown buffer layer on the Ga 2 O 3  substrate;  
         [0037]     forming a first GaN layer on the low temperature-grown buffer layer while providing a N 2  atmosphere in the MOCVD apparatus; and  
         [0038]     forming a second GaN layer on the first GaN layer while providing a H 2  atmosphere in the MOCVD apparatus.  
         [0039]     In the above invention (5), the following modifications and changes can be made.  
         [0040]     (iii) The nitriding step is conducted in a temperature range of 750° C. to 850° C.  
         [0041]     (iv) The low temperature-grown buffer layer comprises Al x Ga 1-x N (0≦x≦1).  
         [0000]     (6) According to another aspect of the invention, a light emitting element comprises:  
         [0042]     a conductive first layer comprising gallium oxides;  
         [0043]     a second layer comprising Al x Ga 1-x N (0≦x≦1) formed under a growth condition to prevent a thermal decomposition of the first layer; and  
         [0044]     a third layer comprising a GaN-based semiconductor formed on the second layer.  
         [0045]     In the above invention (6), the following modifications and changes can be made.  
         [0046]     (v) The second layer is formed under the growth condition in a temperature range of 350° C. to 550° C. and in a H 2  atmosphere.  
         [0047]     (vi) The third layer comprises a first semiconductor layer with a first conductivity type, a second semiconductor layer with a second conductivity type different from the first conductivity type, and a light emitting layer to emit a light based on a current fed through the first semiconductor layer and the second semiconductor layer.  
         [0000]     (7) According to another aspect of the invention, a light emitting device comprises:  
         [0048]     a light emitting element comprising a conductive first layer comprising gallium oxides, a second layer comprising Al x Ga 1-x N (0≦x≦1) formed under a growth condition to prevent a thermal decomposition of the first layer, and a third layer comprising a GaN-based semiconductor formed on the second layer;  
         [0049]     an element mounting portion on which the light emitting element is mounted; and  
         [0050]     a sealing portion that seals the light emitting element and the element mounting portion.  
         [0051]     In the above invention (7), the following modifications and changes can be made.  
         [0052]     (vii) The element mounting portion comprises a substrate of an inorganic material.  
         [0053]     (viii) The element mounting portion comprises a lead of a conductive metal.  
         [0000]     &lt;Advantages of the Invention&gt; 
         [0054]     In the invention, the third GaN-based semiconductor layer with a good crystalline quality can be formed by forming the second Al x Ga 1-x N (0≦x≦1) layer under the growth condition to prevent the thermal decomposition of the first conductive transparent Ga 2 O 3 -based layer. By using the light emitting element thus made, the light emitting device can have an excellent handling property in mounting and a high reliability. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0055]     The preferred embodiments according to the invention will be explained below referring to the drawings, wherein:  
         [0056]      FIG. 1  is a schematic side view showing an LED element in a first preferred embodiment according to the invention;  
         [0057]      FIG. 2  is a schematic process diagram showing a manufacturing process of the LED element in the first preferred embodiment;  
         [0058]      FIG. 3  is a schematic cross sectional view showing a light emitting device in a second preferred embodiment according to the invention; and  
         [0059]      FIG. 4  is a schematic cross sectional view showing a light emitting device in a third preferred embodiment according to the invention. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
     First Embodiment  
       [0060]      FIG. 1  is a schematic side view showing an LED element in the first preferred embodiment according to the invention.  
         [0061]     The LED element  1  as described hereinafter is fabricated by using an MOCVD (=metal organic chemical vapor deposition) apparatus.  
         [0062]     Composition of the LED Element  1   
         [0063]     The LED element  1  comprises, on a n-conductivity type substrate  10  made of β-Ga 2 O 3  (hereinafter called Ga 2 O 3  substrate  10 ), an AlN buffer layer  11  formed under low temperature growth conditions, a Si-doped n + -GaN layer  12 , a Si-doped n-AlGaN layer  13 , an MQW (=multiple-quantum well) of InGaN/GaN, a Mg-doped p-AlGaN layer  15 , a Mg-doped p + -GaN layer  16 , and a current spreading layer  17  of ITO (indium tin oxide). Further, a p-electrode  18  is formed on the surface of the current spreading layer  17 , and an n-electrode  19  is formed on the n + -GaN layer  12  which is partially exposed by etching from the current spreading layer  17  through the n-AlGaN layer  13 .  
         [0064]     The AlN buffer layer  11  is formed by using H 2  carrier gas under temperature conditions of preferably 400° C. to 550° C., and by supplying NH 3  and trimethylaluminum (TMA) into a reactor in which the Ga 2 O 3  substrate  10  is placed.  
         [0065]     The n + -GaN layer  12  and p + -GaN layer  16  are formed by using N 2  carrier gas under temperature conditions of 1050° C., and by supplying NH 3  and trimethylgallium (TMG), GaN source materials, into the reactor in which the Ga 2 O 3  substrate  10  is placed. The n + -GaN layer  12  is doped with Si by using a Si dopant, monosilane (SiH 4 ) to have the n-type conductivity. The p + -GaN layer  16  is doped with Mg by using a Mg dopant, cyclopentadienyl magnesium (Cp 2 Mg) to have the p-type conductivity. The n-AlGaN layer  13  and p-AlGaN layer  15  are formed by supplying the TMA as well as the above GaN source materials into the reactor.  
         [0066]     The MQW  14  is formed by using N 2  carrier gas under temperature conditions of 800° C., and by supplying NH 3 , trimethylindium (TMI) and trimethylgallium (TMG) into the reactor. When the InGaN is formed, NH 3 , TMI and TMG are supplied. When the GaN is formed, NH 3  and TMG are supplied.  
         [0067]      FIG. 2  is a schematic process diagram showing a manufacturing process of the LED element in the first preferred embodiment. In  FIG. 2 , the vertical axis indicates temperature and the horizontal axis indicates time. Each step will be explained below.  
         [0068]     Substrate Cleaning Step  
         [0069]     The Ga 2 O 3  substrate  10  used in this process and 1 cm×2 cm in plane and 350 micrometers in thickness is cleaned with HNO3 at 60° C. for 10 min, then ultrasonic-cleaned in ethanol for 5 min, then ultrasonic-cleaned in pure water for 5 min.  
         [0070]     Nitriding Treatment Step of the Surface of Substrate  
         [0071]     Then, the Ga 2 O 3  substrate  10  cleaned in the substrate cleaning step is placed on a susceptor in the MOCVD apparatus. Then, temperature is risen since time t 1  while supplying N 2  into the reactor. The temperature rise is stopped at time t 1  when reaching 800° C., and this temperature is maintained. The surface of the substrate is nitrided since time t 3  in order to be in stabilization.  
         [0072]     AlN Buffer Layer Forming Step  
         [0073]     Then, the supplying of N 2  into the reactor is stopped at time t 4 , and the supplying of H 2  is begun. Then, temperature rise in the reactor is stopped at time t 5 . At time t 6  when reaching 400° C., TMA is supplied 50 sccm with NH 3  while keeping the reactor temperature at about 400° C. Thereby, the AlN buffer layer  11  with a thickness of 100 to 300 angstroms is formed on the Ga 2 O 3  substrate  10  since time t 7 .  
         [0074]     GaN Forming Step  
         [0075]     Then, the supplying of H 2  into the reactor is stopped at time t 8 , and the supplying of N 2  is begun. Then, temperature rise in the reactor is begun since time t 9  and stopped at time t 10  when reaching 1050° C. Since time t 10 , TMG is supplied 60 sccm with NH 3  while keeping the reactor temperature at 1050° C. Thereby, the n + -GaN layer  12  with a thickness of 1 micrometer is formed on the AlN buffer layer  11 . Then, at time till, the supplying of N 2  into the reactor is stopped and the supplying of H 2  is begun. Thereby, the n + -GaN layer  12  with a thickness of 2 micrometer is further formed on the AlN buffer layer  11 . At time t 12 , the supplying of H 2  into the reactor is stopped.  
         [0076]     Thereafter, the n-AlGaN layer  13 , the MQW layer  14 , the p-AlGaN layer  15 , the p + -GaN layer  16 , the current spreading layer  17 , the p-electrode  18  and n-electrode  19  are fabricated sequentially. Explanations for the process of fabricating these are omitted.  
         [0077]     Observing the surface of the n + -GaN layer  12  thus formed on the AlN buffer layer  11 , it is confirmed that the GaN is obtained with a good flatness. Thus, even when the buffer layer is formed on the Ga 2 O 3  substrate  10  in the H 2  atmosphere, the GaN can be formed with a mirror surface without being thermally damaged. Further, it is confirmed that, when a GaN-based LED structure (=light emitting element) as shown in  FIG. 1  is fabricated on the n + -GaN layer  12 , it emits a blue light with a wavelength of 480 nm in feeding a current of 20 mA.  
         [0078]     Effects of the First Embodiment  
         [0079]     In the first embodiment, by forming the AlN buffer layer  11  on the Ga 2 O 3  substrate  10  in the H 2  atmosphere at a temperature of 350° C. to 550° C., preferably at about 400° C., the AlN buffer layer  11  can be stably formed without being subjected to the thermal decomposition of β-Ga 2 O 3  in the H 2  atmosphere. Thus, the n + -GaN layer  12  with a good crystalline quality can be formed thereon.  
         [0080]     Although in the first embodiment the LED element  1  comprises the AlN buffer layer  11  formed on the Ga 2 O 3  substrate  10 , the buffer layer  11  can have desirably a composition of Al x Ga 1-x N (0≦x≦1), which is defined more desirably (0≦x≦1), most desirably (0.5≦x≦1).  
         [0081]     Although in the first embodiment the temperature of the substrate surface is 800° C. in the nitriding treatment, it is found by the inventors that the n + -GaN layer  12  with a good crystalline quality can be formed at a temperature in the range of 750° C. to 850° C. in the nitriding treatment.  
       Second Embodiment  
       [0082]     Composition of Light Emitting Device  20   
         [0083]      FIG. 3  is a schematic cross sectional view showing a light emitting device in the second preferred embodiment according to the invention.  
         [0084]     The light emitting device  20  is an SMD (surface mount device) type LED. It comprises a ceramics substrate  23  which is of Al 2 O 3  etc. and has patterned wirings  21 ,  22  formed of tungsten (W), a main body  24  which is a sintered body of an inorganic material and is integrated with the ceramics substrate  23 , the LED element  1  in which the n-electrode and p-electrode are electrically connected through wires  25  of Au to the wirings  21 ,  22  exposed at the bottom of the main body  24 , and a phosphor containing silicone resin  27  which contains phosphors  26  and seals the LED element  1 .  
         [0085]     The LED element  1  is, as described in the first embodiment, a face-up type LED element fabricated such that the AlN buffer layer  11  is formed on the Ga 2 O 3  substrate  10  in the H 2  atmosphere, and the LED structure including the MQW etc. is formed thereon, to emit a blue light with a central emission wavelength of about 480 nm in operation.  
         [0086]     The ceramics substrate  23  is provided with the wirings  21 ,  22  of W formed from its joint surface to the main body  24  through its side to a part of the bottom. Thereby, the LED element  1  can be mounted by solder reflowing etc. at the bottom and side thereof.  
         [0087]     The main body  24  is provided with an opening  24 A with a depth reaching the wirings  21 ,  22  from its upper surface. A sidewall  24 B of the opening  24 A has a slope formed to allow the inner diameter of the opening  24 A to be enlarged in the light radiation direction. Further, the sidewall  24 B has a reflection surface (not shown) formed thereon by deposition of Al in order to reflect a light emitted from the LED element  1 .  
         [0088]     The phosphor containing silicone resin  27  contains the phosphor  26  of Ce:YAG (yttrium aluminum garnet) to generate a yellow light when being excited by the blue light emitted from the LED element  1 . Thus, a white light is, in complementary color relationship, produced when the yellow light generated excited by the blue light is mixed with the blue light from the LED element  1 . Alternatively, when a phosphor film is provided on the light extraction surface of the LED element  1  instead of containing the phosphor in the silicone resin, a wavelength conversion type light emitting device can be formed to radiate a white light.  
         [0089]     Effects of the Second Embodiment  
         [0090]     In the second embodiment, a small package LED can be obtained with a good mass productivity while using the LED element  1  as described in the first embodiment. Although the phosphor containing silicone resin  27  is used in the second embodiment, a silicone resin or epoxy resin not containing the phosphor may be used. Furthermore, it may contain a predetermined amount of a filler to reduce the thermal expansion difference to the main body  24 .  
       Third Embodiment  
       [0091]     Composition of Light Emitting Device  20   
         [0092]      FIG. 4  is a schematic cross sectional view showing a light emitting device in the third preferred embodiment according to the invention.  
         [0093]     The light emitting device  20  is a bullet-type LED lamp that the LED element  1  as described in the first embodiment is mounted on a lead frame of Cu Alloy. It comprises lead frames  30 ,  31  which is formed by stamping a Cu alloy material and has a Ag plating on the surface to have a light reflection property, the LED element  1  mounted on the lead frame  31 , a wire  25  which is of Au and connects electrically between the n-electrode and p-electrode of the LED element  1  and the lead frames  30 ,  31 , and a sealing resin  32  which is of transparent epoxy resin to seal integrally the LED element  1 , the wire  25  and the lead frames  30 ,  31 .  
         [0094]     The lead frame  31  is provided with a cup portion  31 A formed by stamping, on which the LED element  1  is mounted. The cup portion  31 A has a sidewall  31 B with a slope formed to allow the inner diameter thereof to be enlarged in the light radiation direction.  
         [0095]     The LED element  1  is secured through adhesives such as Ag paste onto the bottom of the cup portion  31 A, and is sealed with a transparent coating resin  33  which is filled into the cup portion  31 A after the wire bonding to the n-electrode and p-electrode. The coating resin  33  may contain a phosphor such as YAG to generate a yellow light by being excited by a blue light emitted from the LED element  1 .  
         [0096]     Effects of the Second Embodiment  
         [0097]     In the third embodiment, the bullet type LED lamp can be obtained with a good mass productivity while using the LED element  1  as described in the first embodiment. Although in the third embodiment the LED element  1  is secured onto the bottom of the cup portion  31 A formed on the lead frame  31 , it may be secured onto the lead frame  31  without the cup portion  31 A. In this case, the sealing step using the coating resin  33  can be removed. Therefore, the fabrication cost can be reduced.  
         [0098]     Although the invention has been described with respect to the specific embodiments for complete and clear disclosure, the appended claims are not to be thus limited but are to be construed as embodying all modifications and alternative constructions that may occur to one skilled in the art which fairly fall within the basic teaching herein set forth.