Patent Application
20190272994
Implementations of the disclosure generally relate to processes for depositing materials for solar, semiconductor, or other electronic device applications, and more particularly to epitaxial growth of Group III/V materials.
Group III/V materials, such as gallium arsenide or gallium aluminum arsine, may be deposited or formed by epitaxial growth during a chemical vapor deposition (CVD) process. However, epitaxial growth of high quality Group III/V materials is often quite slow. A typical CVD process may epitaxially grow a Group III/V material at a deposition rate within a range from about 1 μm/hr to about 3 μm/hr. The quality of the epitaxial material is generally greatly reduced by slightly increasing the deposition rate. Usually, a Group III/V material grown at a deposition rate of about 5 μm/hr is of low quality and often has structural defects within the crystalline lattice and/or contains amorphous material.
Therefore, there is a need for a deposition process for depositing high quality, epitaxial Group III/V materials at high growth rates (e.g., at least greater than 5 μm/hr).
Implementations of the disclosure generally relate processes for epitaxial growing Group III/V materials at high growth rates or deposition rates, such as about 30 μm/hr or greater, for example, about 40 μm/hr, about 50 μm/hr, about 55 μm/hr, about 60 μm/hr, about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. As used herein, the term “greater” in connection with growth or deposition rates may refer to higher deposition rates including those described within the context of this disclosure. As used herein, the term “about” may indicate an approximate value that can be within ±1%, ±2%, ±3%, ±5%, ±10%, ±15%, or ±20% of a nominal value. Moreover, as used herein, the range 90-120 μm/hr can indicate one or more different growth or deposition rates, including about 90 μm/hr, about 95 μm/hr, about 100 μm/hr, about 105 μm/hr, about 110 μm/hr, about 115 μm/hr, or about 120 μm/hr. The deposited Group III/V materials or films may be utilized in solar, semiconductor, or other electronic device applications. In some implementations, the Group III/V materials may be formed or grown on a sacrificial layer disposed on or over the support substrate during a vapor deposition process. Subsequently, the Group III/V materials may be removed from the support substrate during an epitaxial lift off (ELO) process. The Group III/V materials are thin films of epitaxially grown layers which contain gallium arsenide, gallium aluminum arsenide, gallium indium arsenide, gallium indium arsenide nitride, gallium aluminum indium phosphide, phosphides thereof, nitrides thereof, derivatives thereof, alloys thereof, or combinations thereof. The Group III/V materials can also be referred to as Group III/V semiconductors or Group III/V semiconductor materials.
In one implementation, a method for forming a Group III/V material containing gallium arsenide on a wafer is provided which includes heating the wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas and arsine, and depositing a gallium arsenide layer on the wafer at a deposition rate of about 30 μm/hr or greater. As used herein, the term “30 μm/hr or greater” can refer to, for example, growth or deposition rates of about 40 μm/hr, about 50 μm/hr, about 55 μm/hr, about 60 μm/hr, about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. Moreover, as used herein, the term “greater” in connection with deposition temperatures may refer to higher temperatures including those described within the context of this disclosure. In another implementation, the wafer is heated to a deposition temperature of about 650° C. or greater within a processing system, and exposed to a deposition gas containing a gallium precursor gas, an aluminum precursor gas, and arsine. A Group III/V material containing a gallium aluminum arsenide layer is grown at a deposition rate of about 30 μm/hr or greater. For the 90-120 μm/hr deposition rates, the range of the deposition temperature can be between about 680° C. and about 850° C.
In another implementation, a method includes heating the wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, and arsine, and depositing a Group III/V layer or material on the wafer at a deposition rate of about 30 μm/hr or greater (e.g., 90-120 μm/hr deposition rates). The Group III/V layer or material contains gallium, arsenic, and indium. In one example, the deposition temperature is within a range from about 650° C. to about 800° C. In some examples, the gallium precursor gas contains trimethylgallium and the indium precursor gas contains trimethylindium. For the 90-120 μm/hr deposition rates, the range of the deposition temperature can be between about 680° C. and about 850° C.
In some implementations, the deposition rate or growth rate may be about 40 μm/hr or greater, such as about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater (e.g., 90-120 μm/hr deposition rates). In other implementations, the deposition temperature may be about 600° C. or greater, or may be about 700° C. or greater, or may be about 800° C. or greater, or may be about 850° C. In some examples, the deposition temperature may be within a range from about 550° C. to about 900° C. In other examples, the deposition temperature may be within a range from about 600° C. to about 800° C. In other examples, the deposition temperature may be within a range from about 650° C. to about 750° C. In other examples, the deposition temperature may be within a range from about 650° C. to about 720° C. For the 90-120 μm/hr deposition rates, the range of the deposition temperature can be between about 680° C. and about 850° C.
In another implementation, a method includes heating the wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, a nitrogen precursor gas, and arsine, depositing a Group III/V layer or material on the wafer at a deposition rate of about 30 μm/hr or greater (e.g., 90-120 μm/hr deposition rates), wherein the Group III/V layer or material contains gallium, arsenic, indium, and nitrogen. The nitrogen precursor gas may contain hydrazine, methylhydrazine, dimethylhydrazine, derivatives thereof, or combinations thereof. In one example, the nitrogen precursor gas contains dimethylhydrazine. In another example, the nitrogen precursor gas contains hydrazine. In some examples, the gallium precursor gas contains trimethylgallium and the indium precursor gas contains trimethylindium. For the 90-120 μm/hr deposition rates, the range of the deposition temperature can be between about 680° C. and about 850° C.
In another implementation, a method includes heating the wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, an aluminum precursor, and a phosphorus precursor, depositing a Group III/V layer or material on the wafer at a deposition rate of about 30 μm/hr or greater (e.g., 90-120 μm/hr deposition rates), wherein the Group III/V layer or material contains gallium, indium, aluminum, and phosphorus. In one example, the gallium precursor contains trimethylgallium, the aluminum precursor contains trimethylaluminum, the indium precursor contains trimethylindium, and the phosphorus precursor contains phosphine. For the 90-120 μm/hr deposition rates, the range of the deposition temperature can be between about 680° C. and about 850° C.
So that the manner in which the above recited features of the disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to implementations, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical implementations of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective implementations.
The following description is presented to enable one of ordinary skill in the art to make and use the disclosure and is provided in the context of a patent application and its requirements. Various modifications to the preferred implementations and the generic principles and features described herein will be readily apparent to those skilled in the art. Thus, the present disclosure is not intended to be limited to the implementations shown, but is to be accorded the widest scope consistent with the principles and features described herein.
Implementations of the disclosure generally relate processes for epitaxial growing Group III/V materials at high growth rates, such as about 30 μm/hr or greater, for example, about 40 μm/hr, about 50 μm/hr, about 55 μm/hr, about 60 μm/hr, about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. The deposited Group III/V materials or films may be utilized in solar, semiconductor, or other electronic device applications. These electronic device applications may include applications that involve optoelectronic devices, components, or modules. In some implementations, the Group III/V materials may be formed or grown on a sacrificial layer disposed on over the support substrate during a vapor deposition process. Subsequently, the Group III/V materials may be removed from the support substrate during an epitaxial lift off (ELO) process, for example. The Group III/V materials are thin films of epitaxially grown layers which contain gallium arsenide, gallium aluminum arsenide, gallium indium arsenide, gallium indium arsenide nitride, gallium aluminum indium phosphide, phosphides thereof, nitrides thereof, derivatives thereof, alloys thereof, or combinations thereof.
In one implementation, a method for forming a Group III/V material containing gallium arsenide on the wafer is provided which includes heating a wafer to a deposition temperature of about 550° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas and arsine, and depositing a gallium arsenide layer on the wafer at a deposition rate of about 30 μm/hr or greater.
In another implementation, a method for forming a Group III/V material containing gallium aluminum arsenide is provided which includes heating the wafer to a deposition temperature of about 650° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an aluminum precursor gas, and arsine, and depositing a gallium aluminum arsenide layer at a deposition rate of about 30 μm/hr or greater. In one example, the Group III/V material contains an n-type gallium aluminum arsenide layer having the chemical formula of Al0.3Ga0.7As.
In another implementation, a method for forming a Group III/V material on a wafer or substrate is provided which includes heating a wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, and arsine, and depositing a Group III/V layer on the wafer at a deposition rate of about 30 μm/hr or greater. The Group III/V layer contains gallium, arsenic, and indium. In one example, the deposition temperature is within a range from about 650° C. to about 800° C. In some examples, the gallium precursor gas contains trimethylgallium and the indium precursor gas contains trimethylindium.
In another implementation, a method for forming a Group III/V material on a wafer or substrate is provided which includes heating a wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, a nitrogen precursor gas, and arsine, depositing a Group III/V layer on the wafer at a deposition rate of about 30 μm/hr or greater, wherein the Group III/V layer contains gallium, arsenic, indium, and nitrogen. The nitrogen precursor gas may contain hydrazine, methylhydrazine, dimethylhydrazine, derivatives thereof, or combinations thereof. In one example, the nitrogen precursor gas contains dimethylhydrazine. In another example, the nitrogen precursor gas contains hydrazine. In some examples, the gallium precursor gas contains trimethylgallium and the indium precursor gas contains trimethylindium.
In another implementation, a method for forming a Group III/V material on a wafer or substrate is provided which includes heating a wafer to a deposition temperature of about 600° C. or greater within a processing system, exposing the wafer to a deposition gas containing a gallium precursor gas, an indium precursor gas, an aluminum precursor, and a phosphorus precursor, depositing a Group III/V layer on the wafer at a deposition rate of about 30 μm/hr or greater, wherein the Group III/V layer contains gallium, indium, aluminum, and phosphorus. In one example, the gallium precursor contains trimethylgallium, the aluminum precursor contains trimethylaluminum, the indium precursor contains trimethylindium, and the phosphorus precursor contains phosphine.
In some implementations, the deposition rate or growth rate may be about 40 μm/hr or greater, such as about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater (e.g., about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr). In other implementations, the deposition temperature may be about 600° C. or greater, or may be about 700° C. or greater, or may be about 800° C. or greater, or may be about 850° C. In some examples, the deposition temperature may be within a range from about 550° C. to about 900° C. In other examples, the deposition temperature may be within a range from about 600° C. to about 800° C. In other examples, the deposition temperature may be within a range from about 650° C. to about 750° C. In other examples, the temperature may be within a range from about 650° C. to about 720° C. In other examples, such as for deposition rates of about 90-120 μm/hr, the deposition temperature may be within a range from about 680° C. to about 850° C.
The gallium precursor gas may contain an alkyl gallium compound. In one example, the alkyl gallium compound may be trimethylgallium or triethylgallium. In some implementations, the deposition gas may further contain an aluminum precursor gas and the gallium arsenide layer further contains aluminum. The aluminum precursor gas may contain an alkyl aluminum compound, such as trimethylaluminum or triethylaluminum. In other implementations, the deposition gas contains the arsine and the gallium precursor gas at an arsine/gallium precursor ratio of about 3 or greater, or may be about 4 or greater, or may be about 5 or greater, or may be about 6 or greater, or may be about 7 or greater. In some examples, the arsine/gallium precursor ratio may be within a range from about 5 to about 10. In other implementations, the Group III/V materials may be formed or grown from a deposition gas containing a ratio of Group V precursor to Group III precursor of about 30:1, or 40:1, or 50:1, or 60:1, or greater. In some examples, the deposition gas has a phosphine/Group III precursor of about 50:1.
The processing system may have an internal pressure within a range from about 20 Torr to about 1,000 Torr. In some implementations, the internal pressure may be ambient or greater than ambient, such as within a range from about 760 Torr to about 1,000 Torr. In some examples, the internal pressure may be within a range from about 800 Torr to about 1,000 Torr. In other examples, the internal pressure is within a range from about 780 Torr to about 900 Torr, such as from about 800 Torr to about 850 Torr. In other implementations, the internal pressure may be ambient or less than ambient, such as within a range from about 20 Torr to about 760 Torr, preferably, from about 50 Torr to about 450 Torr, and more preferably, from about 100 Torr to about 250 Torr.
In some implementations, the deposition gas further contains a carrier gas. The carrier gas may contain hydrogen (H2), nitrogen (N2), a mixture of hydrogen and nitrogen, argon, helium, or combinations thereof. In many examples, the carrier gas contains hydrogen, nitrogen, or a mixture of hydrogen and nitrogen.
In general, the flow rates for the various gases used in the deposition process may depend on the chemical vapor deposition (e.g., metal-organic chemical vapor deposition or MOCVD) tool used for the process.
Wafer 112 may be a support substrate containing Group III/V materials, and may be doped with various elements. Generally wafer 112 contains gallium arsenide, alloys thereof, derivatives thereof, and may be an n-doped substrate or a p-doped substrate. In many examples, wafer 112 is a gallium arsenide substrate or a gallium arsenide alloy substrate. The gallium arsenide substrate or wafer may have a thermal expansion coefficient of about 5.73×10−6° C.−1.
Buffer layer 114 may be a gallium arsenide buffer layer which contains gallium arsenide, alloys thereof, dopants thereof, or derivatives thereof. Buffer layer 114 may have a thickness within a range from about 100 nm to about 1000 nm, such as about 200 nm or about 300 nm. In some instances, the buffer layer 114 is a gallium arsenide buffer layer in a range from about 50 nm to about 2000 nm.
Sacrificial layer 116, also referred to as the ELO release layer, may contain aluminum arsenide, alloys thereof, derivatives thereof, or combinations thereof. Sacrificial layer 116 may have a thickness of about 20 nm or less. In some examples the thickness of sacrificial layer 116 may be within a range from about 1 nm to about 20 nm, such as from about 5 nm to about 20 nm, or in other examples, from about 1 nm to about 10 nm, such as from about 4 nm to about 6 nm.
Gallium arsenide cell 110 further contains n-type gallium arsenide stack 120 disposed on or over p-type gallium arsenide stack 130. N-type dopants used may include Si, Te, and Se, and p-type dopants used may include C, Zn, and Mg. The n-type gallium arsenide stack 120 usually contains multiples layers of various n-type doped materials. In one implementation, n-type gallium arsenide stack 120 contains emitter layer 126 disposed on or over passivation layer 124, disposed on or over contact layer 122. In some implementations, the n-type gallium arsenide stack 120 may have a thickness within a range from about 200 nm to about 1,300 nm.
Contact layer 122 may be a gallium arsenide contact layer which contains gallium arsenide, alloys thereof, dopants thereof, or derivatives thereof. In some examples, contact layer 122 contains an n-type gallium arsenide material. Contact layer 122 may have a thickness within a range from about 5 nm to about 100 nm, such as about 10 nm or about 50 nm.
Passivation layer 124, also referred to as the front window, generally contains aluminum gallium arsenide, alloys thereof, derivatives thereof, or combinations thereof. In many examples, passivation layer 124 contains an n-type aluminum gallium arsenide material. In one example, passivation layer 124 contains an n-type aluminum gallium arsenide material having the chemical formula of Al0.3Ga0.7As. Passivation layer 124 may have a thickness within a range from about 5 nm to about 100 nm, such as about 10 nm or about 50 nm.
Emitter layer 126 may contain gallium arsenide, alloys thereof, derivatives thereof, or combinations thereof. In many examples, emitter layer 126 contains an n-type gallium arsenide material. Emitter layer 126 may have a thickness within a range from about 100 nm to about 3000 nm. In some examples the thickness of emitter layer 126 may be within a range from about 100 nm to about 600 nm, such as from about 200 nm to about 400 nm, or in other examples, from about 600 nm to about 1,200 nm, such as from about 800 nm to about 1,000 nm.
The p-type gallium arsenide layer or stack 130 usually contains multiples layers of various p-type doped materials. In one implementation, p-type gallium arsenide stack 130 contains contact layer 136 disposed on or over passivation layer 134, disposed on or over absorber layer 132. In an alternative implementation, absorber layer 132 is absent from p-type gallium arsenide stack 130. Therefore, p-type gallium arsenide stack 130 contains contact layer 136 disposed on or over passivation layer 134, and passivation layer 134 may be disposed on or over n-type gallium arsenide stack 120, emitter layer 126, or another layer. In some implementations, the p-type gallium arsenide stack 130 may have a thickness within a range from about 100 nm to about 3,000 nm.
Absorber layer 132 may contain gallium arsenide, alloys thereof, derivatives thereof, or combinations thereof. In many examples, absorber layer 132 contains a p-type gallium arsenide material. In one implementation, absorber layer 132 may have a thickness within a range from about 1 nm to about 3,000 nm. In some examples the thickness of absorber layer 132 may be within a range from about 1 nm to about 1,000 nm, such as from about 10 nm to about 100 nm, or in other examples, from about 1,000 nm to about 3,000 nm, such as from about 1,100 nm to about 2,000 nm. In some examples the thickness of absorber layer 132 may be within a range from about 100 nm to about 600 nm, such as from about 200 nm to about 400 nm, or in other examples, from about 600 nm to about 1,200 nm, such as from about 800 nm to about 1,000 nm.
Passivation layer 134, also referred to as the rear window, generally contains aluminum gallium arsenide, alloys thereof, derivatives thereof, or combinations thereof. In many examples, passivation layer 134 contains a p-type aluminum gallium arsenide material. In one example, passivation layer 134 contains a p-type aluminum gallium arsenide material having the chemical formula of Al0.3Ga0.7As. Passivation layer 134 may have a thickness within a range from about 25 nm to about 100 nm, such as about 50 nm or about 300 nm.
Contact layer 136 may be a p-type gallium arsenide contact layer which contains gallium arsenide, alloys thereof, dopants thereof, or derivatives thereof. In some examples, contact layer 136 contains a p-type gallium arsenide material. Contact layer 136 may have a thickness within a range from about 5 nm to about 100 nm, such as about 10 nm or about 50 nm.
Aspects of the deposition processes for depositing or forming Group III/V materials, as described herein, may be conducted in a processing system such as, for example, a single wafer deposition chamber, a multi-wafer deposition chamber, a stationary deposition chamber, or a continuous feed deposition chamber. One continuous feed deposition chamber that may be utilized for depositing or forming Group III/V materials is described in the commonly assigned U.S. Ser. No. 12/475,131 (titled “Methods and Apparatus for a Chemical Vapor Deposition Reactor”) filed on May 29, 2009, and U.S. Ser. No. 12/475,169 (titled “Methods and Apparatus for a Chemical Vapor Deposition Reactor” filed on May 29, 2009 and issued as U.S. Pat. No. 8,602,707, each of which is herein incorporated by reference.
In one implementation, a deposition gas may be formed by combining or mixing two, three, or more chemical precursors within a gas manifold prior to entering or passing through the showerhead. In another implementation, the deposition gas may be formed by combining or mixing two, three, or more chemical precursors within a reaction zone after passing through the showerhead. The deposition gas may also contain one, two or more carrier gases, which may also be combined or mixed with the precursor gases prior to or subsequent to passing through the showerhead. The carrier gas may be hydrogen, nitrogen, argon, or combinations thereof. The internal pressure of the deposition chamber may be within a range from about 250 Torr to about 450 Torr.
Example 1—GaAs: In one example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG) and an arsenic precursor (e.g., arsine). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In one example, the deposition temperature may be within a range from about 600° C. to about 800° C., such as from about 650° C. to about 750° C. or from about 650° C. to about 720° C. In one example, the deposition gas may contain about 100 cc of arsine in about 2,000 cc of hydrogen gas (H2) and about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2. The Group III/V material contains gallium and arsenic and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 2—GaAlAs: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an aluminum precursor (e.g., TMA), and an arsenic precursor (e.g., arsine). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In one example, the deposition temperature may be within a range from about 600° C. to about 800° C. In one example, the deposition gas may contain about 100 cc of arsine in about 2,000 cc of hydrogen gas; about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2); and about 200 cc of TMA/H2 (about 1% TMA in H2). The Group III/V material contains gallium, aluminum, and arsenic and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 3—AlGaInP: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an aluminum precursor (e.g., TMA), an indium precursor (e.g., trimethylindium—TMI), and a phosphorus precursor (e.g., phosphine—PH3). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In one example, the deposition temperature may be within a range from about 600° C. to about 800° C. In one example, the deposition gas may contain about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2); about 200 cc of TMA/H2 (about 1% TMA in H2); about 200 cc of TMI/H2 (about 1% TMI in H2); and about 100 cc of phosphine in about 2,000 cc of hydrogen gas. The Group III/V material contains gallium, aluminum, indium, and phosphorus and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 4—GaInAs: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an indium precursor (e.g., trimethylindium), and an arsenic precursor (e.g., arsine). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In an example, the deposition temperature may be within a range from about 600° C. to about 800° C. In one example, the deposition gas may contain about 100 cc of arsine in about 2,000 cc hydrogen gas; about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2); and about 200 cc of TMI/H2 (about 1% TMI in H2). The Group III/V material contains gallium, indium, and arsenic and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 5—GaInAsN: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an indium precursor (e.g., trimethylindium), an arsenic precursor (e.g., arsine), and a nitrogen precursor (e.g., dimethylhydrazine or hydrazine). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In an example, the deposition temperature may be within a range from about 400° C. to about 500° C., such as about 450° C. In one example, the deposition gas may contain about 10 cc of arsine in about 2,000 cc of hydrogen gas; about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2); about 200 cc of TMI/H2 (about 1% TMI in H2); and about 100 cc of dimethylhydrazine in about 1,000 cc of hydrogen gas. The Group III/V material contains gallium, indium, aluminum, arsenic, and nitrogen and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 6—GaInAsP: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an indium precursor (e.g., trimethylindium), an arsenic precursor (e.g., arsine), and a phosphorus precursor (e.g., phosphine—PH3). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. In an example, the deposition temperature may be within a range from about 600° C. to about 800° C. In one example, the deposition gas may contain about 100 cc of arsine in about 2,000 cc of hydrogen gas; about 200 cc of a mixture of TMG/H2 (about 10% TMG in H2); about 200 cc of TMI/H2 (about 1% TMI in H2); and about 100 cc of phosphine in about 2,000 cc of hydrogen gas. The Group III/V material contains gallium, indium, arsenic, and phosphorus, and may be deposited at a rate of about 30 μm/hr or greater, such as about 40 μm/hr or greater, preferably, about 50 μm/hr or greater, preferably, about 55 μm/hr or greater, and more preferably, about 60 μm/hr or greater. In an example, deposition rates greater than about 60 μm/hr can include deposition rates of about 70 μm/hr, about 80 μm/hr, or about 90-120 μm/hr. For the deposition rates of about 90-120 μm/hr the deposition temperature can be in the range from about 680° C. to about 850° C.
Example 7—InGaP: In another example, the deposition gas may be formed by combining a gallium precursor (e.g., TMG), an indium precursor (e.g., trimethylindium), and a phosphorus precursor (e.g., phosphine—PH3). The substrate may be heated to a deposition temperature and exposed to the deposition gas. The deposition temperature can have a wide range. The Group III/V material in this example contains gallium, indium, and phosphorus, and may be deposited at high growth rates (e.g., at or greater than 8 μm/hr) to form InGaP layers for a solar cell (referred to as an InGaP solar cell). For example, layers of InGaP compounds may be deposited at a deposition rate selected from the group consisting of 8 μm/hr, 10 μm/hr, 20 μm/hr, 30 μm/hr, and a range of 8-120 μm/hr deposition rates. The InGaP solar cell can be n-on-p or p-on-n or n-i-p in design. The InGaP solar cell may be a front-junction device or a rear-junction device. A p-n junction in the InGaP solar cell may be formed as a homo-junction with InGaP on both sides of the junction grown at fast growth rate, or as a hetero-junction with InGaP on one-side of the junction and AlGaInP, AlInP, AlGaAs, or a similar alloy on the other side of the junction.
In the examples described above, the term “cc” may refer to cubic centimeters and may correspond to a flow rate or flow unit, such as a standard cubic centimeters per minute (sccm).
At block 210, the method 200 includes heating a wafer to a deposition temperature in a range between 550° C. and 900° C. within a processing system.
At block 220, the method 200 includes exposing the wafer to a deposition gas comprising a gallium precursor gas and arsine at a total pressure in a range between 20 Torr and 1000 Torr.
At block 230, the method 200 includes depositing one or more layers having gallium arsenide on the wafer at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, wherein multiple layers, including the one or more layers, form a gallium arsenide cell. The gallium arsenide cell may be used in an optoelectronic device (e.g., photovoltaic or solar cell) or in an electronic device (e.g., transistors).
In an aspect of the method 200, for the 90-120 μm/hr deposition rates the range of the deposition temperature can be between 680° C. and 850° C.
In another aspect of the method 200, the deposition gas can further include an aluminum precursor gas and the gallium arsenide layer can further include aluminum. The aluminum precursor gas can include an alkyl aluminum compound. The alkyl aluminum compound can be trimethylaluminum or triethylaluminum.
In another aspect of the method 200, the deposition gas can further include a carrier gas comprising a mixture of hydrogen and argon.
In another aspect of the method 200, an n-type portion of the gallium arsenide cell is deposited over a sacrificial layer having a thickness between 1 nm and 20 nm, where the sacrificial layer is disposed over a buffer layer, and the buffer layer is disposed over the wafer.
In another aspect of the method 200, the multiple layers form an n-type gallium arsenide stack and a p-type gallium arsenide stack, where the n-type gallium arsenide stack has an emitter layer disposed on or over a first passivation layer, and where the first passivation layer is disposed on or over a first contact layer; and where the p-type gallium arsenide stack has a second contact layer disposed on or over a second passivation layer, and where the second passivation layer being disposed on or over an absorber layer.
In another aspect of the method 200, the range of the deposition temperature can be between 600° C. and 800° C.
In another aspect of the method 200, the range of the total pressure can be selected from the group consisting of between 20 Torr and 760 Torr, between 50 Torr and 450 Torr, and between 100 Torr and 250 Torr.
At block 310, the method 300 includes heating a wafer to a deposition temperature in a range between 550° C. and 900° C. within a processing system.
At block 320, the method 300 includes exposing the wafer to a deposition gas comprising a gallium precursor gas, an aluminum precursor gas, and arsine at a total pressure in a range between 20 Torr and 1000 Torr.
At block 330, the method 300 includes depositing one or more layers on the wafer at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, where the one or more layers include aluminum gallium arsenide, and multiple layers, including the one or more layers, form an aluminum gallium arsenide cell. The aluminum gallium arsenide cell may be used in an optoelectronic device (e.g., photovoltaic or solar cell) or in an electronic device (e.g., transistors).
In an aspect of the method 300, for the 90-120 μm/hr deposition rates the range of the deposition temperature is between 680° C. and 850° C.
In another aspect of the method 300, an n-type portion of the gallium arsenide cell is deposited over a sacrificial layer having a thickness between 1 nm and 20 nm, where the sacrificial layer is disposed over a buffer layer, and where the buffer layer is disposed over the wafer.
In another aspect of the method 300, the multiple layers form an n-type gallium arsenide stack and a p-type gallium arsenide stack, where the n-type gallium arsenide stack has an emitter layer disposed on or over a first passivation layer, and where the first passivation layer is disposed on or over a first contact layer; and where the p-type gallium arsenide stack has a second contact layer disposed on or over a second passivation layer, and where the second passivation layer is disposed on or over an absorber layer.
In another aspect of the method 300, the range of the deposition temperature can be between 600° C. and 800° C.
In another aspect of the method 300, the range of the total pressure can be selected from the group consisting of between 20 Torr and 760 Torr, between 50 Torr and 450 Torr, and between 100 Torr and 250 Torr.
At block 410, the method 400 includes heating a wafer to a deposition temperature in a range between 550° C. and 900° C. within a processing system.
At block 420, the method 400 includes exposing the wafer to a deposition gas comprising a gallium precursor gas, an indium precursor gas, a nitrogen precursor gas and arsine at a total pressure in a range between 20 Torr and 1000 Torr.
At block 430, the method 400 includes depositing one or more layers on the wafer at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, where the one or more layers comprise gallium, arsenic, nitrogen and indium, and multiple layers, including the one or more layers, form a GaInAsN cell. The GaInAsN cell may be used in an optoelectronic device (e.g., photovoltaic or solar cell) or in an electronic device (e.g., transistors).
In an aspect of the method 400, for the 90-120 μm/hr deposition rates the range of the deposition temperature is between 680° C. and 850° C.
In another aspect of the method 400, the nitrogen precursor gas comprises a compound selected from the group consisting of hydrazine, methylhydrazine, dimethylhydrazine, derivatives thereof, and combinations thereof.
In another aspect of the method 400, an n-type portion of the gallium arsenide cell is deposited over a sacrificial layer having a thickness between 1 nm and 20 nm, where the sacrificial layer is disposed over a buffer layer, and where the buffer layer is disposed over the wafer.
In another aspect of the method 400, the multiple layers form an n-type gallium arsenide stack and a p-type gallium arsenide stack, where the n-type gallium arsenide stack has an emitter layer disposed on or over a first passivation layer, and where the first passivation layer is disposed on or over a first contact layer; and where the p-type gallium arsenide stack has a second contact layer disposed on or over a second passivation layer, and where the second passivation layer is disposed on or over an absorber layer.
In another aspect of the method 400, the deposition temperature can be between 400° C. and 500° C.
In another aspect of the method 400, the range of the total pressure can be selected from the group consisting of between 20 Torr and 760 Torr, between 50 Torr and 450 Torr, and between 100 Torr and 250 Torr.
At block 510, the method 500 includes heating a substrate comprising gallium and arsenic to a temperature in a range between 550° C. and 900° C. within a processing system.
At block 520, the method 500 includes exposing the substrate to a deposition gas comprising a gallium arsenide precursor gas and arsine.
At block 530, the method 500 includes depositing an n-type contact layer comprising gallium and arsenic over the substrate, where the n-type contact layer has a thickness of 100 nm or less.
At block 540, the method 500 includes depositing an n-type passivation layer comprising gallium, aluminum, and arsenic over the substrate, where the n-type passivation layer has a thickness of 100 nm or less.
At block 550, the method 500 includes depositing an n-type absorber layer comprising gallium and arsenic over the substrate, where the n-type emitter layer has a thickness of 3000 nm or less.
At block 560, the method 500 includes depositing a p-type passivation layer comprising gallium, aluminum, and arsenic over the substrate, where the p-type passivation layer has a thickness of 300 nm or less.
At block 570, the method 500 includes depositing a p-type contact layer comprising gallium and arsenic over the substrate, the p-type contact layer having a thickness of 100 nm or less, where each of the n-type contact layer, the n-type passivation layer, the n-type absorber layer, the p-type passivation layer, and the p-type contact layer is deposited at deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates.
In another aspect of the method 500, for the 90-120 μm/hr deposition rates the range of the deposition temperature is between 680° C. and 850° C.
In another aspect of the method 500, the method further includes depositing a sacrificial layer comprising aluminum and arsenic over the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, where the sacrificial layer has a thickness of 20 nm or less. The method can further include depositing the n-type contact layer over the sacrificial layer, depositing the n-type passivation layer over the n-type contact layer, depositing the n-type absorber layer over the n-type passivation layer, depositing the p-type passivation layer over the p-type absorber layer, and depositing the p-type contact layer over the p-type passivation layer.
In another aspect of the method 500, the method further includes depositing a buffer layer comprising gallium and arsenic on the substrate at a deposition rate selected from the group consisting of a 30 μm/hr deposition rate, a 40 μm/hr deposition rate, a 50 μm/hr deposition rate, a 55 μm/hr deposition rate, and a 60 μm/hr deposition rate or greater, where the buffer layer has a thickness of less than 300 nm. The can further include depositing the sacrificial layer over the buffer layer.
In another aspect of the method 500, the method further includes depositing a sacrificial layer comprising aluminum and arsenic over the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, where the sacrificial layer has a thickness of 20 nm or less.
In another aspect of the method 500, the method further includes depositing a buffer layer comprising gallium and arsenic on the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, where the buffer layer has a thickness of less than 300 nm. The method can further include depositing the sacrificial layer over the buffer layer.
In another aspect of the method 500, exposing the substrate to the deposition gas further includes exposing the substrate to a total pressure of 450 Torr or less, or exposing the substrate to a total pressure of at least 780 Torr.
At block 610, the method 600 includes heating a wafer to a deposition temperature in a range between 550° C. and 900° C. within a processing system.
At block 620, the method 600 includes exposing the wafer to a deposition gas comprising a gallium precursor gas, an indium precursor gas, and phosphine at a total pressure in a range between 20 Torr and 1000 Torr.
At block 630, the method 600 includes depositing one or more layers having InGaP on the wafer at a deposition rate selected from the group consisting of 8 μm/hr, 10 μm/hr, 20 μm/hr, 30 μm/hr, and a range of 8-120 μm/hr deposition rates, wherein multiple layers, including the one or more layers, form an InGaP solar cell.
In another aspect of the method 600, for the 8-120 μm/hr deposition rates the range of the deposition temperature may be between 550° C. and 900° C.
In another aspect of the method 600, the InGaP solar cell is a metamorphic structure where the one or more InGaP layers are grown mismatched to the wafer, wherein the wafer is a GaAs substrate.
In another aspect of the method 600, the InGaP has a range of compositions represented by InxGa1-xP with x being the composition of indium, wherein the indium composition is in a range between 30% to 70% when the one or more InGaP layers are mismatched to the wafer and the wafer is a GaAs substrate, and wherein the indium composition is 50%+/−4% when the one or more InGaP layers are lattice-matched to GaAs.
In another aspect of the method 600, the InGaP cell is part of an optoelectronic device or an electronic device. The optoelectronic device may include a light-emitting diode (LED), a laser, a transistor-laser, a photodetector, or a photovoltaic, including a solar cell. The electronic device is a transistor and the transistor is one of a heterojunction bipolar transistor (HBT), a high electron mobility transistor (HEMT), a quantum well field effect transistor (QWFET), or a pseudomorphic HEMT (pHEMT).
In another aspect of the method 600, the gallium precursor gas and the indium precursor gas includes one or more of TMIn, TEIn, TMGa, TEGa, PH3, or TBP (tert-butylphosphine).
In another aspect of the method 600, the deposition gas further comprises a carrier gas comprising a mixture of hydrogen and argon.
In another aspect of the method 600, the InGaP cell is deposited over a sacrificial layer having a thickness between 1 nm and 200 nm, the sacrificial layer being disposed over a buffer layer, the buffer layer having a thickness in a range of 50 nm to 200 nm, and the buffer layer being disposed over the wafer. The sacrificial layer may be made of one of AlAs, AlInP, AlGaAs, AlInGaP, or InGaP.
In another aspect of the method 600, the multiple layers form an n-type InGaP stack and a p-type InGaP stack, the n-type InGaP stack having an emitter layer disposed on or over a first passivation layer, the first passivation layer being disposed on or over a first contact layer, and the p-type InGaP stack having a second contact layer disposed on or over a second passivation layer, the second passivation layer being disposed on or over an absorber layer.
In another aspect of the method 600, the InGaP cell forms an n-on-p solar cell, a p-on-n solar cell, am n-i-p solar cell, or a p-i-n solar cell.
In another aspect of the method 600, the InGaP cell is a front-junction device or a rear-junction device. A front junction device may refer to a device having a p-n junction closer to a side of the device that receives the light and a rear junction device may refer to a device having a p-n junction closer to a side of the device away from a side of the device that receives the light.
In another aspect of the method 600, the InGaP cell includes one or more p-n junctions, and at least one of the one or more p-n junctions is a homojunction with InGaP on both sides of the junction.
In another aspect of the method 600, the InGaP cell includes one or more p-n junctions, and at least one of the one or more p-n junctions is a heterojunction with InGaP on one side and AlGaInP, AlGaAs, or AlInP on the other side, wherein the AlGaInP, AlGaAs, or AlInP is deposited at a deposition rate selected from the group consisting of 8 μm/hr, 10 μm/hr, 20 μm/hr, 30 μm/hr, and a range of 8-120 μm/hr deposition rates.
In another aspect of the method 600, the InGaP cell includes a graded junction and at least one of the one or more layers having InGaP is part of the graded junction.
In another aspect of the method 600, the range of the deposition temperature is between 600° C. and 800° C.
In another aspect of the method 600, the range of the total pressure is selected from the group consisting of: between 20 Torr and 760 Torr, between 50 Torr and 450 Torr, and between 100 Torr and 250 Torr.
In another aspect of the method 600, the method 600 is performed as part of a metal organic chemical vapor deposition (MOCVD) process that uses reactors with or without a showerhead configuration.
In another aspect of the method 600, a bubbler temperature for the indium precursor gas is in the range of 15° C. to 60° C.
In another aspect of the method 600, the deposition rate under V/III ratios of 1 to 300. This is basically refers to how much Group V gases (like PH3) flow in comparison to sum of Group III gases (like TMIn+TMGa). That is, the V/III ratio is a simple representation of a ratio of gas flows: PH3/(TMGa+TMIn) for example in the case of InGaP.
At block 710, the method 700 includes heating a substrate comprising gallium and arsenic to a temperature in a range between 550° C. and 900° C. within a processing system.
At block 720, the method 700 includes exposing the substrate to a deposition gas comprising a gallium precursor gas and arsine.
At block 730, the method 700 includes depositing an n-type contact layer comprising gallium and arsenic over the substrate, where the n-type contact layer has a thickness of 100 nm or less.
At block 740, the method 700 includes depositing a first passivation layer comprising one or more of the following elements aluminum, gallium, indium, and/or phosphorous over the substrate, where the first passivation layer has a thickness of 100 nm or less. The first passivation may be an n-type passivation.
At block 750, the method 700 includes depositing an n-type or p-type absorber layer comprising one or more of the following elements gallium, indium, aluminum, and/or phosphorous over the substrate, where an n-type or p-type emitter layer has a thickness of 2000 nm or less.
At block 760, the method 700 includes depositing a second passivation layer having one or more of the following elements gallium, indium, aluminum, and/or phosphorous, where the second passivation layer has a thickness of 2000 nm or less.
At block 770, the method 700 includes depositing a p-type contact layer comprising one or more of the following elements aluminum, gallium, and arsenic over the substrate, the p-type contact layer having a thickness of 100 nm or less, where each of the n-type contact layer, the first passivation layer, the n-type or p-type absorber layer, the second passivation layer, and the p-type contact layer is deposited at deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and a range of 8-120 μm/hr deposition rates. An n-type of p-type emitter layer may be deposited using the same depositing rates as described above.
In another aspect of the method 700, the compounds having gallium, indium, aluminum, and/or phosphorous may be deposited at a deposition rate selected from the group consisting of 8 μm/hr, 10 μm/hr, 20 μm/hr, 30 μm/hr, and a range of 8-120 μm/hr deposition rates. An n-type of p-type emitter layer may include one or more of the materials described above and may be deposited using the same depositing rates as described above.
In another aspect of the method 700, for the 8-120 μm/hr deposition rates the range of the deposition temperature is between 550° C. and 900° C.
In another aspect of the method 700, the method 700 further includes depositing a sacrificial layer comprising aluminum and arsenic over the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, the sacrificial layer having a thickness of 200 nm or less; depositing the n-type contact layer over the sacrificial layer; depositing the first passivation layer over the n-type contact layer; depositing the n-type or p-type absorber layer over the first passivation layer; depositing the second passivation layer over the n-type of p-type absorber layer; and depositing the p-type contact layer over the second passivation layer.
In another aspect of the method 700, the method 700 further includes depositing a buffer layer comprising gallium and arsenic on the substrate at a deposition rate selected from the group consisting of a 30 μm/hr deposition rate, a 40 μm/hr deposition rate, a 50 μm/hr deposition rate, a 55 μm/hr deposition rate, and a 60 μm/hr deposition rate or greater, the buffer layer having a thickness in a range between 50 nm and 2000 nm; and depositing the sacrificial layer over the buffer layer.
In another aspect of the method 700, the method 700 further includes depositing a sacrificial layer comprising aluminum and arsenic over the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, the sacrificial layer having a thickness of 200 nm or less. Moreover, a buffer layer may be deposited comprising gallium and arsenic on the substrate at a deposition rate selected from the group consisting of 30 μm/hr, 40 μm/hr, 50 μm/hr, 55 μm/hr, 60 μm/hr, 70 μm/hr, 80 μm/hr, and 90-120 μm/hr deposition rates, the buffer layer having a thickness in a range between 50 nm and 2000 nm; and the sacrificial layer may be deposited over the buffer layer.
In another aspect of the method 700, exposing the substrate to a deposition gas further comprises exposing the substrate to a total pressure of 450 Torr or less, or exposing the substrate to a total pressure of at least 780 Torr.
In another aspect of the method 700, depositing an n-type or p-type emitter layer having a thickness of 2000 nm or less.
While the foregoing is directed to implementations of the disclosure, other and further implementations of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application is a Continuation-in-Part of non-provisional patent application Ser. No. 15/717,694, filed Sep. 27, 2017, which is a Continuation-in-Part of non-provisional patent application Ser. No. 12/904,090, filed Oct. 13, 2010, which claims under 35 USC 119(e), the benefit of provisional patent application Ser. No. 61/251,677, filed Oct. 14, 2009. Each of these applications is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61251677 | Oct 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15717694 | Sep 2017 | US |
| Child | 16412328 | US | |
| Parent | 12904090 | Oct 2010 | US |
| Child | 15717694 | US |
