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  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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Definitions

• This invention relates to a method for growing improved quality devices using low temperature magnesium doped nitride films.
• GaN gallium nitride
• MOCVD metalorganic chemical vapor deposition
• HVPE hydride vapor phase epitaxy
• Nitride based optoelectronic devices began their quick ascent to commercialization with the advent of the use of a thin nucleation layer prior to the deposition of high quality GaN [1,2]. This technique is employed due to the lack of a native substrate available for GaN growth. More recently, techniques such as the development of p-type GaN by magnesium doping followed by high temperature annealing have also proved vital.
• InGaN indium gallium nitride
• LEDs nitride based light emitting diodes
• LDs laser diodes
• FIG. 1 illustrates a typical deposition temperature profile as a function of deposition time for fabricating a nitride based diode device.
• Most nitride LED and LD processes using MOCVD begin by heating the substrate to a temperature of approximately 1050 0 C for 5-30 minutes (referred to as the "Bake” step in FIG. 1). This initial step is believed to aid in the removal of any impurities that might be present on the surface of the sapphire (AI 2 O 3 ) substrate and substrate holder. The temperature is then lowered to between 450-700 0 C to grow the low temperature GaN nucleation layer (NL) (referred to as the "NL" step in FIG. 1). Most nucleation layers are deposited to a thickness of approximately 10-50 run.
• NL GaN nucleation layer
• the substrate temperature is increased to approximately 1050 0 C for the deposition of high quality GaN thin films (referred to as the "GaN: Si” step in FIG. 1).
• This GaN film can be doped with silicon (Si) to achieve n-type conductivity for the electrically negatively charged material because of the over abundance of electrically active electrons that are present.
• the substrate temperature is decreased to deposit the InGaN multiple quantum well (MQW) (referred to as the "MQW” step in FIG. 1 ).
• MQW InGaN multiple quantum well
• Typical substrate temperatures for InGaN deposition range from 700-900 0 C and are dependent on growth conditions and reactor geometry. Above this temperature range, indium nitride (InN) becomes volatile and easily dissociates leading to low InN incorporation in the films. Below this temperature, InN incorporation greatly increases which can lead to indium clustering and poor film quality.
• InN indium nitride
• an AlGaN electron blocking layer is usually deposited on top of the MQW. Typical thicknesses for this layer range from 5 nm to 300 nm.
• the AlGaN film acts as an electron blocking layer when the LED is biased. This is due to the larger bandgap energy of the AlGaN present in the layer, wherein the AlGaN layer acts as a potential energy barrier that the electrons must overcome, thereby aiding in the confinement of the electrons to the active region of the device. This confinement increases the probability of radiative recombination in the active region of the LED [4].
• the film is then heated to a substrate temperature between 1000 0 C to 1100 0 C in order to deposit a film of p-type GaN doped with magnesium (Mg) (referred to as the "GaN:Mg" step in FIG. 1).
• Mg p-type GaN doped with magnesium
• Typical thicknesses for the Mg doped GaN films range from 150 nm to 500 nm.
• Mg incorporation into GaN has been shown to act as a deep level acceptor, causing the Mg doped nitride material to have a lack of electrons which results in the film having an electrically positive behavior (p-type GaN).
• Mg doped GaN has been extensively used in nitride based LEDs, the use comprises of GaN films grown at temperatures higher than the deposition temperature of the preceding InGaN MQWs.
• InN has a high volatility and readily evaporates out of the InGaN films when exposed to a high enough temperature and/or a low temperature for an extended period of time. This time and temperature value is commonly referred to as the material's thermal budget.
• the present invention distinguishes itself from the above-mentioned methods by the use of a low temperature (LT) Mg doped nitride layer in order to improve the quality of diodes and devices comprising InN.
• LT low temperature
• the present invention discloses a method for growing an improved quality device by depositing a low temperature (LT) magnesium (Mg) doped nitride semiconductor thin film.
• the low temperature Mg doped nitride semiconductor thin film may have a thickness greater than 50nm.
• the low temperature Mg doped semiconductor thin film may comprise one or more layers of intentionally doped or unintentionally doped materials.
• the method may further comprise depositing one or more Indium containing nitride based quantum well layers at a growth temperature, and depositing a nitride semiconductor film, for example, a LT Mg doped nitride semiconductor thin film, on the quantum well layers at a growth substrate temperature no greater than 150 0 C above the growth temperature of the Indium containing nitride-based quantum well layers.
• the nitride semiconductor film may comprise one or more layers of intentionally doped or unintentionally doped materials, nitride semiconductor thin film may have a thickness greater than 50nm.
• the nitride semiconductor film may comprise multiple layers having varying or graded compositions.
• the nitride semiconductor film may comprise a heterostructure comprising layers of dissimilar (Al,Ga,In,B)N composition.
• the nitride semiconductor film may comprise GaN, AlN, InN, AlGaN, InGaN or AlInN.
• the nitride semiconductor thin film may be grown in any crystallographic nitride direction, such as on a conventional c-plane oriented nitride semiconductor crystal, or on a nonpolar plane such as a-plane or m-plane, or on any semipolar plane.
• the growth substrate temperature may be substantially equal to the growth temperature, or no greater than 50 0 C above the growth temperature of the Indium containing nitride-based quantum well layers .
• the nitride semiconductor film and the Indium containing nitride-based quantum well layers may be grown by hydride vapor phase epitaxy (HVPE), metalorganic chemical vapor deposition (MOCVD), or molecular beam epitaxy (MBE).
• HVPE hydride vapor phase epitaxy
• MOCVD metalorganic chemical vapor deposition
• MBE molecular beam epitaxy
• the present invention further discloses a device having enhanced output power.
• the device may be a light emitting diode (LED), comprising one or more Indium containing nitride-based quantum well layers, an n-type layer deposited on one side of the Indium containing nitride-based quantum well layers for injecting n-type carriers into the Indium containing nitride-based quantum well layers, and a nitride semiconductor layer, containing Mg, deposited on the Indium containing nitride-based quantum well layers for acting as a p-type layer, wherein the nitride semiconductor layer has a thickness of at least 50 nm.
• LED light emitting diode
• FIG. 1 shows a typical temperature profile for the deposition of a nitride based diode device containing InGaN multiple quantum wells.
• FIG. 2 is a flow chart of the method for growing a Mg-doped nitride film according to the preferred embodiment of this invention.
• FIG. 3 shows the temperature profile for the deposition of a nitride based diode device comprising InGaN multiple quantum wells, according to the preferred embodiment of this invention.
• FIG. 4 shows LED output power as a function of the Mg doped GaN growth temperature.
• FIG. 5 shows the dependence of LED output power on the Mg doped GaN thickness.
• the present invention describes a method for growing device-quality, planar LT Mg doped nitride semiconductor thin films via MOCVD. Growth of LT Mg doped nitride semiconductor layers offers a means of improving device characteristics in Ill-nitride structures.
• nitrides refers to any alloy composition of the (Ga,Al,In,B)N semiconductors having the formula where:
• Current nitride devices such as LEDs and LDs, comprise a high temperature grown (Al,In,Ga,B)N Mg doped layer .
• the high temperature Mg doped layer deposition results in a drastic degradation in device performance such as device output power.
• Growth of LT Mg doped (Al,In,Ga,B)N layers could improve device performance by greatly minimizing the thermal budget exerted on the previously deposited (Al,In,Ga,B)N films.
• the present invention provides a means of enhancing (Al,In,Ga,B)N device performance by use of LT Mg doped layers grown by MOCVD.
• the present invention describes a method for growing device-quality planar LT Mg doped nitride semiconductor thin films via MOCVD.
• Growth of LT Mg doped nitride semiconductor layers offers a means of improving device characteristics in Ill-nitride structures. These films were grown using a commercially available MOCVD system.
• General growth parameters for LT Mg doped GaN growth comprise a pressure between 10 torr and 1000 torr and a temperature less than 150 0 C above the MQW temperature.
• the epitaxial relationships and conditions should hold true regardless of the type of reactor used. However, the reactor conditions for growing LT Mg doped GaN will vary according to individual reactors and growth methods (HVPE, MOCVD, and MBE, for example).
• the InGaN 's thermal budget can be greatly decreased by growing the Mg doped GaN film at a temperature less than or equal to that used to grow the MQW.
• the deposition temperature of the Mg doped GaN film grown after the diode's MQW which typically contains 1-20% InN in GaN, it is possible to reduce the thermal damage to the MQW material. This greatly increases the MQWs quality by maintaining sha ⁇ heterojunction interfaces and decreasing InN segregation and clustering.
• the method for growing a nitride film according the present invention generally comprises the following steps: ( 1 ) Loading the substrate into an MOCVD reactor.
• TMGa trimethylgallium
• the temperature set point is decreased for the deposition of the InGaN MQW.
• TMIn trimethylindium
• TMGa trimethylindium
• TMGa trimethylaluminium
• the LT Mg doped planar nitride semiconductor thin film may comprise of GaN, AlN, InN, AlGaN, InGaN or AlInN, for example.
• the LT Mg doped planar nitride semiconductor thin film may comprise multiple layers having varying or graded compositions.
• the LT Mg doped planar nitride semiconductor thin film may comprise a heterostructure containing layers of dissimilar (Al,Ga,In,B)N composition.
• FIG. 2 is a flowchart that illustrates the steps for the growth of LT Mg doped gallium nitride (GaN) thin films using MOCVD, according to the preferred embodiment of the present invention that is described in the following paragraphs.
• Block 200 represents the step of loading a substrate, wherein a sapphire (0001) substrate may be loaded into an MOCVD reactor.
• Block 202 represents the step of heating the substrate under hydrogen and/or nitrogen and/or ammonia flow. During this step, the reactor's heater is turned on and ramped to a set point temperature of 1150 0 C under hydrogen and/or nitrogen and/or ammonia flow. Generally, nitrogen and/or hydrogen flow over the substrate at atmospheric pressure.
• Block 204 represents the step of depositing a nucleation layer. During this step, twenty minutes after ramping to the set point temperature of Block 202, the reactor's set point temperature is decreased to 570 0 C and 3 seem of TMGa is introduced into the reactor to initiate the GaN nucleation or buffer layer growth. After 100 seconds, the GaN nucleation or buffer layer reaches the desired thickness. At this point, the TMGa flow is shut off and the reactor's temperature is increased to 1185 0 C.
• Block 206 represents the step of depositing an n-type nitride semiconductor film. During this step, once the set point temperature of block 204 is reached, 15 seem of TMGa may be introduced into the reactor to initiate the GaN growth for 15 minutes. Once the desired GaN thickness is achieved, 4sccm OfSi 2 He is introduced into the reactor to initiate the growth of n-type GaN doped with silicon for 45 minutes.
• Block 208 represents the step of depositing one or more nitride based active layers on a substrate at a growth temperature.
• the active layers may be, for example, one or more quantum wells or multi quantum wells, and preferably contain Indium (In), for example, 1-20% InN in GaN.
• the reactor's temperature set point is decreased to 880 0 C, and 30 seem of TEGa is introduced into the reactor for 200 seconds to initiate the deposition of the GaN barrier layer.
• 70 seem of TMIn is introduced into the reactor for 24 seconds and then shut off, to initiate the deposition of the InGaN quantum well layer.
• Block 210 represents the step of depositing an electron blocking layer. During this step, once the MQW of Block 208 is deposited, 1 seem of TMGa and 1 seem of TMAl are introduced into the reactor for 100 seconds and then shut off, for the deposition of the AlGaN electron blocking layer.
• Block 212 represents the step of depositing a nitride semiconductor film on the active layers at a substrate temperature no greater than 150 0 C or 50 0 C above the growth temperature, wherein the nitride semiconductor film preferably comprises an LT nitride semiconductor film doped with Mg. During this step, once the desired AlGaN thickness of Block 210 is achieved, the reactor's set point temperature is maintained at 880 0 C and 3.5 seem of TMGa and 50 seem of
• Block 214 represents the step of annealing the film in a hydrogen (H) deficient atmosphere. During this step, once the reactor has cooled in Block 212, the nitride diode is removed and annealed in a hydrogen deficient atmosphere for 15 minutes at a temperature of 700 0 C in order to activate the LT Mg doped GaN.
• H hydrogen
• Block 216 represents the end result of the method, for example, a device having enhanced output power.
• the device is a nitride- based LED or Laser Diode (LD) including LT Mg doped GaN.
• the device may be an LED comprising one or more Indium containing nitride-based quantum well layers, an n-type layer deposited on one side of the Indium containing nitride-based quantum well layers for injecting n-type carriers into the Indium containing nitride-based quantum well layers, and a nitride semiconductor layer, containing Mg, deposited on the Indium containing nitride-based quantum well layers for acting as a p-type layer, wherein the nitride semiconductor layer has a thickness of at least 50 nm.
• steps may be omitted or added as desired.
• Blocks 204 and 210 maybe omitted as desired.
• FIG. 3 shows the deposition temperature profile as a function of deposition time for the preferred embodiment of this invention.
• nitride LED and LD processes using MOCVD begin by heating the substrate to a temperature of approximately 1050 0 C (referred to as the "Bake” step in FIG. 3). The temperature may then be lowered to between 450-700 0 C to grow the low temperature GaN nucleation layer (referred to as the "NL" step in FIG. 3). Once a desired nucleation layer (NL) thickness is achieved, the substrate temperature may be increased to approximately 1050 0 C for the deposition of high quality GaN thin films (referred to as the "GaN:Si" step in FIG. 3).
• the substrate temperature may be decreased to deposit the InGaN multiple quantum well (MQW) (referred to as the "MQW” step in FIG. 3).
• MQW InGaN multiple quantum well
• Typical substrate temperatures for InGaN deposition range from 700-900 0 C and are dependent on growth conditions and reactor geometry.
• an AlGaN electron blocking layer is optionally deposited on top of the MQW.
• a LT film of p-type GaN doped with Mg may be deposited (referred to as the "GaNrMg" step in FIG. 3).
• the temperature for growth of the Mg doped GaN film (the "GaNrMg” step in FIG. 3) is the same as the temperature for the growth of the MQW that was previously deposited in the "MQW” step of FIG. 3.
• the LT Mg doped GaN deposition temperature is drastically different in comparison to what is used in current nitride technology.
• FIG. 4 shows the measured dependence of LEDs' output power on Mg doped
• GaN deposition temperature The output power of the LEDs was evaluated by measuring the light output using a silicon photo detector through the back of the substrate. This is commonly referred to as an "on-wafer" measurement. It is important to note that the MQW deposition temperature for all the LEDs in FIG. 4 was 880 0 C. It is clear from the FIG. 4 data that using a deposition temperature for the Mg doped GaN similar to the deposition temperature for the MQW can drastically improve the output power of the LED. The maximum output power was observed for a LT Mg doped deposition temperature of 880 0 C.
• the output power of the LEDs is significantly reduced with a Mg doped GaN deposition temperature greater than the MQW deposition temperature (880 0 C), with the lowest output power measured for a LT Mg doped deposition temperature of 950 0 C. It may be concluded that using an LT Mg doped GaN deposition temperature, as described in the preferred embodiment of this invention, offers a means of appreciably increasing the output power of a nitride LED.
• FIG. 5 describes the measured output power, or electroluminescence (EL), of LEDs as a function of LT Mg doped GaN thickness. It can be seen that in order to increase the power output of an LED, the thickness of the LT Mg doped GaN needs to exceed 50 nm. In addition, employing the use of a LT Mg doped GaN layer which has a thickness greater than 100 nm can significantly improve the power output even further.
• EL electroluminescence
• the nitride semiconductor film may comprise GaN, AlN, InN, AlGaN, InGaN or AlInN. Moreover, the nitride semiconductor film may be a heterostructure comprising layers of dissimilar (Al,Ga,In,B)N composition.
• Both the nitride semiconductor film and the active layer may be grown in any crystallographic nitride direction, such as on a conventional c-plane oriented nitride semiconductor crystal, or on a nonpolar plane such as a-plane or m-plane, or on any semipolar plane.
• the nitride semiconductor film may be doped with Mg.
• the nitride semiconductor film may include one or more layers of intentionally doped or unintentionally doped materials.
• the nitride semiconductor film is a substantially planar film having a thickness preferably greater than 50 ran and more preferably greater than 100 nm, although other thicknesses may be used.
• the nitride semiconductor film may be comprised of multiple layers having varying or graded compositions.
• the substrate temperature may be substantially equal to the growth temperature and the growth temperature may be 880 0 C.
• the process steps may comprise, and the nitride semiconductor film and active layers may be grown using, for example, HVPE, MOCVD or MBE.
• the final result of the method is a device having enhanced output power.
• the device may be an LED, for example, comprising: one or more nitride active layers containing indium, an n-type layer on one side of the active layers for injecting n-type carriers into the active layers, and a nitride semiconductor layer, containing Mg and on the active layers, acting as a p-type layer.
• the LED may have an output power of at least S milliwatts.

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