Method for passivating a compound semiconductor surface

Abstract: A method for passivating the surface of a compound semiconductor (12) comprises annealing the substrate (12) to form an anion rich surface layer containing cationic and anionic oxides and stripping the oxides to leave only a very thin anionic layer on the surface. The substrate (12) is then subjected to an H₂ plasma cleaning to remove chemisorbed oxygen. An N₂ plasma cleaning is then performed to form an anionic nitride layer (20) that is free of any cationic nitride. A layer of insulating material (22), such as, a native or other oxide, or a nitride, is deposited. The resulting structure (10) has a very low interface state density such that the Fermi level may be swept through the entire band gap.

Description: This invention relates to semiconductor structures having a compound semiconductor-insulator interface and a method for passivating compound semiconductor surfaces prior to deposition of an insulating material. Recently, there has been extensive technological research in the area of growing insulating materials such as oxides and nitrides onto compound semiconductor substrates such as GaAs. The driving force behind this research is to realize MOS devices on III-V compound semiconductor substrates. Heretofor, attempts to fabricate MOS structures on GaAs have been unsuccessful due to the very high density of interface states which are nearly always present on exposed GaAs surfaces or at interfaces with virtually all materials. The presence of the high density of interface states causes the pinning of the GaAs interface Fermi level. In the fabrication of MOS structures on III-V substrates, the surface Fermi level should be unpinned to allow the Fermi level to be varied by bias voltages applied to the gate electrode. The movement of the Fermi level permits the device to be operated in an inversion mode or an accumulation mode, depending on the polarity of the bias applied to the gate. Previous attempts to deposit insulators onto compound semiconductor substrate surfaces have been largely unsuccessful due to the insulator-substrate interface defects. For example, the GaAs surface is composed of two oxides, As₂O₃ and Ga₂O₃. The As₂O₃ is of poor quality and can act metallic. The Ga₂O₃ is a high quality oxide that is stable up to 500°C. These surface oxides are approximately 2 to 3 nanometers thick. The GaAs surface presents problems because of the poor thermal stability of As₂O₃ and because free arsenic is present on the GaAs surface. Prior attempts have been made passivate the compound semiconductor surface prior to deposition of an insulating material. U.S. Patent 4,645,683 teaches treating a GaAs substrate in a hydrogen and arsine multipolar plasma to remove the oxides. The substrate is then treated in a nitrogen multipolar plasma to provide a protective layer of gallium nitride and arsenic nitride. Silicon nitride is then deposited onto the protective layer. Attempts to improve this process have included an initial chemical cleaning in a solution of hydrochloric acid to reduce the oxide thickness prior to the plasma treatments, as shown by Friedel, et al, "Photoemission Study of the Passivation of GaAs in a Nitrogen Multipolar Plasma." Philosophical Magazine, Vol. 55, pp. 711-719, 1987. Friedel, et al. recognize that a very high density of interface states still exists precluding MOSFET applications. The present invention is directed to a method for passivating a compound semiconductor surface by forming a layer of anionic nitride its on the surface of the compound semiconductor substrate that is free of any detectable amounts of its cationic nitride. In accordance with the invention, the anionic nitride layer is formed by annealing the substrate to form an anion rich surface layer that contains cationic and anionic oxides. The cationic and anionic oxides are then stripped from the surface leaving an anionic layer on the surface of the compound semiconductor. The oxides are typically stripped by a wet etch process using dilute hydrochloric acid. After the etch, the substrate is transferred in air to a plasma reactor. During the transfer, oxygen is chemisorbed by the substrate, most likely in the arsenic layer. In the reactor, the substrate is subjected to a plasma cleaning in hydrogen which is preferably a low pressure, low voltage treatment. The hydrogen cleaning removes any chemisorbed species from the anionic layer. The substrate is then subjected to a plasma cleaning in nitrogen also preferably at a low pressure and low voltage. The N₂ nitriding of the anionic layer forms an anionic nitride layer on the surface of the substrate. This anionic layer is free from detectable amounts of cationic nitride. The nitridization step passivates the elemental arsenic thereby reducing the surface charge. In addition, no oxides are present on the surface. Thereafter, an insulating material is deposited onto the passivated compound semiconductor surface. The insulating material is preferably deposited in situ, by electron beam evaporation in a low voltage, low pressure plasma, by sputtering or by PECVD techniques. The passivation of the compound semiconductor surface reduces the density of interface states to a very low level to permit the Fermi level to be swept through the entire band gap. The resulting insulating films are uniform and transparent. Thus, the fabrication of MOSFET devices on GaAs substrates may now be realized. One way of carrying out the invention is described in detail below with reference to drawings which illustrate only one specific embodiment, in which: Figure 1 is a cross sectional view of a semiconductor structure of the present invention. Figure 2 is a schematic of the scheme for the hydrogen and nitrogen plasma cleaning and for depositing an insulating layer onto the compound semiconductor surface. Figure 3 is a graph showing the capacitance vs. voltage characteristics of a structure of the present invention. In accordance with the method of the invention, the surface of the compound semiconductor substrate is passivated by forming a very thin layer of its anionic nitride that is free of detectable amounts of its cationic nitride on the surface of the compound semiconductor. A layer of insulating material is deposited on the anionic nitride layer. The interface between the insulating material and the substrate has a very low density of states so that the Fermi level may be swept through the entire band gap. The invention will be described in more detail hereinafter with respect to a substrate of gallium arsenide. However, it should be understood that the inventive method is applicable to any compound semiconductor material including any other III-V compounds and any II-VI compounds. A substrate of bulk gallium arsenide is passivated in accordance with the invention by first annealing the substrate in a temperature range of 300-500°C. The substrate is preferably annealed in a nitrogen or argon atmosphere. The gallium arsenide substrate surface prior to annealing is composed of arsenic oxide and gallium oxide. After the annealing, the surface layer becomes arsenic rich and contains gallium oxide and small amounts of arsenic oxide. The majority of the arsenic oxide will be transformed into elemental arsenic in accordance with the following formula: As₂O₃ + 2GaAs Ga₂O₃ + 4As The gallium oxide formed from the above reaction combines with the gallium oxide already present on the surface to form a layer containing a large amount of gallium oxide with arsenic and small amounts of arsenic oxide. The resulting structure is then subjected to a wet etch in dilute HCl which strips the gallium oxide and the arsenic oxide leaving an extremely thin layer of arsenic. The layer of arsenic is on the order of one monolayer. After the etch, the substrate is transferred in air which causes oxygen to be chemisorbed by the substrate. It is likely that the oxygen is chemisorbed in the arsenic layer. Although oxygen is chemisorbed, there are no arsenic or gallium oxides present on the substrate. The substrate is then introduced into a plasma reactor where it is subjected to a plasma cleaning in hydrogen at a temperature in the range of 150 to 300°C, preferably at 200°C. The H₂ plasma cleaning is preferably performed at low pressure and low voltage. Typically, the H₂ plasma is performed in a range of 0.13 to 1.33 Pa (1 to 10 mTorr), preferably at 0.67 pa (5 mTorr) and at a voltage in the range of -50 to -250 volts dc, preferably at -150 volts dc. The H₂ plasma reduces the GaAs surface by stripping any chemisorbed oxygen from the surface. Preferably, the H₂ plasma is an RF plasma process. The surface layer is free from gallium and arsenic oxides, however, the elemental arsenic is not depleted. Thus, the monolayer of arsenic on the surface of the gallium arsenic substrate remains. The substrate is then subjected to a RF plasma cleaning in N₂, also preferably at low pressure and low voltage. The range of the N₂ plasma conditions are identical to the range of conditions set forth above for the H₂ plasma. In addition, it is preferred that the N₂ and H₂ plasmas be performed in situ. The surface of the substrate after the H₂ plasma containing the monolayer of elemental arsenic is highly reactive. The RF nitridization will passivate the GaAs surface by forming a layer of arsenic nitride. Since nitrogen has the same valence as arsenic, As-N bonds will form. Thus, the elemental arsenic is passivated which has the result of reducing the surface charge of the structure. Typically, the charge will be reduced from 10¹³ eV/cm² to 10¹¹ eV/cm². The AsN layer is free from any detectable amounts of gallium nitride. Thus, the passivated gallium arsenide substrate is provided with a surface that is suitable for deposition of an insulating material. The gallium arsenide surface is passivated by the AsN layer to the extent that the density of states present at the semiconductor/insulator interface is low enough to permit the Fermi level to be swept through the entire band gap. As shown in Figure 1, the structure 10 includes a gallium arsenide substrate 12 having a first major surface 14 and a second major surface 16. A metallic contact, such as, AuGeNi, may be formed on the surface 16 during the initial annealing step. The substrate 12, after having the surface 14 passivated in accordance with the method of the present invention, includes a very thin layer of arsenic nitride 20. An insulation layer 22 is deposited onto the arsenic nitride layer 20, which in the illustrative embodiment in Figure 1 is gallium oxide. A gate contact 24 is deposited onto the oxide layer 22 to complete the structure. The gallium oxide layer 22 is preferably deposited by electron beam evaporation in a low voltage, low pressure O₂ plasma. As shown in Figure 2, the scheme for E-beam evaporation includes a chamber 26 having a cathode 28 coupled to an RF source 30. A passivated gallium arsenide substrate 32 is positioned in contact with the cathode 28. A crucible 34 containing pure gallium 36 is placed in the chamber and an O₂ plasma is created by introducing oxygen through line 38, which causes Ga₂O₃ to be reactively deposited onto the passivated gallium arsenide substrate. In a preferred embodiment, the substrate is passivated in situ in chamber 26 by first creating a hydrogen plasma by opening line 40 and then creating a nitrogen plasma by closing line 40 and opening line 42. The pressure and voltage ranges for the deposition of the oxide are preferably 0.13 to 1.33 Pa (1 to 10 mTorr) and -50 to -250 volts dc, respectively. Temperature conditions are in the range of 24 to 260°C. The gallium oxide layer is uniform and transparent and can be grown to a thickness of 100 nanometers or more. Sample oxides have been deposited at thicknesses ranging from 95 to 110 nanometers across a 51 mm wafer. Ellipsometry analysis shows that the oxides have an index of refraction in the range between 1.50 to 1.90. In accordance with the practice of the invention, a substrate of bulk gallium arsenide was annealed at 450°C. An AuGeNi metallic contact was alloyed during this step on one surface of the substrate. On the opposite surface of the substrate, an x-ray photoelectron spectroscopy analysis (XPS) revealed that the surface contained substantial amounts of gallium oxide together with small amounts of arsenic oxide and elemental arsenic. The substrate was then dipped in a dilute HCl solution to etch the gallium and arsenic oxides from the surface. XPS tests indicated that no oxides were present with only a very thin layer of arsenic remaining. After the etch, the substrate was transferred in air which caused oxygen to be chemisorbed on the substrate. XPS analysis showed no arsenic or gallium oxide present. The substrate was then introduced into a plasma reactor where it was subjected to the plasma cleaning in hydrogen with the substrate held at a temperature of 200°C. The hydrogen was at a pressure of 5 mTorr and the voltage applied was -150 volts dc. The H₂ plasma cleaning was performed for one minute. XPS analysis of the substrate after the H₂ cleaning indicated no oxygen present. The substrate was then subjected to a plasma nitridization in N₂ with the substrate being held at a temperature of 200°C. The pressure was again 0.67 Pa (5 mTorr) and the voltage -150 volts dc. The N₂ plasma cleaning was also performed for one minute. The XPS results showed a shoulder indicating arsenic nitride. The results indicated that the arsenic nitride layer was free from detectable amounts of gallium nitride. Thereafter, a layer of Ga₂O₃ was deposited by electron beam evaporation of pure gallium through a low voltage, low pressure O₂ plasma. The plasma pressure was 0.26 Pa (2 mTorr) at -100 volts dc. The temperature was 24°C. Ellipsometry analysis indicated that the oxide had an index of refraction of 1.58. The thickness of the oxide layer was approximately 75 nanometers. Auger analysis indicated only the presence of gallium and oxygen with no arsenic. The gallium oxide deposition should preferably take place in situ to prevent interface contamination due to air exposure. After the deposition of the oxide, a thin AsN layer remains at the interface. A gold contact was deposited onto the gallium oxide surface to form an MOS diode and a bias voltage was applied to the structure. Figure 3 shows the MOS capacitance vs. voltage plot for a frequency of 1MHz. The transition from depletion to accumulation is sharp. From accumulation, the dielectric constant ε i , of Ga₂O₃ can be derived using C acc = ε i εA/t ox , where A is the diode area and t ox is the oxide thickness. For t ox = 75nm and A = 3.84 x 10-3 cm⁻², ε i is found to be 8.3. The minimum capacitance Cmin is evaluated according to: C min ≃ ε i t ox + (ε i /ε s ) m m 4ε s KT n (N d /n i ) q² N d Where, ε s is equal to 12.9, N d is the dopant and is equal to 2 x 10¹⁷ cm⁻³ and n i is the intrinsic carrier concentration and is equal to 1.79 x 10⁶ cm⁻³, C min is found to be 205pF, which is very close to the capacitance measured from Figure 3. Thus, devices for intergrated circuits may be fabricated having a gallium oxide interlevel insulator due to its low dielectric constant. In addition, the gallium oxide will not etch in a F⁺ containing plasma so that the oxide will make an excellent reactive ion etching mask. The present invention provides a method for passivating the surface of a compound semiconductor in which the surface is pretreated with an annealing step and a wet etch step which leaves a monolayer of arsenic on the surface. The substrate with the monolayer of arsenic is then subjected to an H₂ plasma cleaning and a N₂ plasma cleaning resulting in the substrate having an arsenic nitride layer that is very thin. A layer of insulating material such as gallium oxide, SiO₂, Al₂O₃, AlN or Si₃N₄, is then deposited. The passivation results in the density of interface states being extremely low which allows the Fermi level to be swept through entire band gap.

Claims: A method for passivating the surface (14) of a compound semiconductor substrate (12) comprising the step of: forming a layer of the anionic nitride (20) of said compound semiconductor, the layer (20) being free of any detectable amount of the cationic nitride of said compound semiconductor on the surface (14) of the compound semiconductor substrate (12), said formation of the anionic nitride of the compound semiconductor including the steps of: annealing said substrate (12) to form a cationic oxide of said compound semiconductor having anions and anionic oxides of said compound semiconductor included therein, removing said oxides leaving said anions on said substrate surface in the form of a thin layer, transporting said substrate in air to a plasma reactor, cleaning said surface in a H₂ plasma in the plasma reactor to remove the oxygen chemisorbed during said air transport from said thin layer, and converting said thin layer of anions to a layer of anionic nitride (20) in a plasma of nitrogen in the plasma reactor. The method according to Claim 1 wherein the substrate (12) is annealed at a temperature range of 300-500°C, preferably of 450-470°C. The method according Claims 1 or 2 wherein the substrate (12) is annealed in an inert atmosphere. The method according to one or more of the preceding Claims 1 to 3 further including the step of forming a metallic contact (18) to an opposing surface (16) of said substrate (12) during the annealing step. The method according to one or more of the preceding Claims 1 to 4 wherein the removing step consists of subjecting the surface to a wet etch in a dilute HCl solution. The method according to one or more of the preceding Claims 1 to 5 wherein the cleaning step in the H₂ plasma to remove any chemisorbed oxygen consists of etching in an RF plasma of hydrogen at low pressure and low voltage. The method according to Claim 6 wherein the H₂ RF plasma is at a pressure in the range of 0.13 to 1.33 Pa (1-10 mTorr), preferably at 0.67 PA (5 mTorr), at a voltage in the range of -50 to -250 volts dc, preferably at -150 volts dc, and at a temperature in the range of 150-300°C, preferably at 200°C. The method according to one or more of the preceding Claims 1 to 7 wherein the converting step in the N₂ plasma consists of using an N₂ RF plasma at low pressure and low voltage. The method according to Claim 8 wherein the N₂ RF plasma is at a pressure in the range 0.13 to 1.33 Pa (1-10 mTorr), preferably at 0.67 Pa (5 mTorr), at a voltage in the range of -50 to -200 volts dc, preferably at -150 volts dc, and at a temperature in the range of 150-300°C, preferably at 200°C. The method according to one or more of the preceding Claims 1 to 9 wherein the cleaning and converting steps are performed in situ. The method according to one or more of the preceding Claims 1 to 10 further including the step of depositing an insulator (22) on said anionic nitride layer (20). The method according to Claim 11 wherein said insulator (22) is deposited by electron beam evaporation. The method according to Claim 12 wherein said electron beam evaporation is a low voltage, low pressure O₂ plasma. The method according to Claim 13 wherein the plasma is at a pressure in the range of 0.13 to 1.33 Pa (1 to 10 mTorr), preferably at 0.266 Pa (2 mTorr), the voltage is in the range of -50 to -250 volts dc, preferably at -100 volts dc, and the temperature is in the range of 24 to 260°C, preferably at 200°C. The method according to one or more of the preceding Claims 11 to 14 wherein the cleaning, converting and insulator depositing steps are performed in situ. The method according to one or more of the preceding Claims 1 to 15 wherein the compound semiconductor (12) is GaAs and the anionic nitride layer (20) is therefore AsN. The method according to one or more of the preceding Claims 11 to 16 wherein the insulator (22) is one of Ga₂O₃, SiO₂, Al₂O₃, AlN, and Si₃N₄.

Inventors: BUCHANAN DOUGLAS ANDREW, CALLEGARI ALLESSANDRO CESARE, HOH PETER DAVID, LACEY DIANNE LYNN, BUCHANAN, DOUGLAS ANDREW, CALLEGARI, ALLESSANDRO CESARE, HOH, PETER DAVID, LACEY, DIANNE LYNN
Applicants: IBM, INTERNATIONAL BUSINESS MACHINES CORPORATION
Application year: 1989
Main classification: H01L21
IPC codes: H01L29, H01L21