This invention relates generally to the field of optical and electronic technology and more particularly to application of Schottky contacts on ZnO and MgxZn1-xO films to be used on various semiconductor devices such as Schottky type UV photodetectors, Schottky diodes and Metal Semiconductor Field Effect Transistors (MESFETs) and more.
Recently, there has been an increasing interest in high quality ZnO films due to the electrical and optical properties of ZnO. These properties include wide and direct energy bandgap (Eg ˜3.3 eV at room temperature) and large photoresponse, a high free exciton bounding energy, availability of a native substrate, ability to be wet chemical-processed, ability to be grown below the temperature of 400° C., as well as having high resistance to radiation damage. In the past, an optically addressed high contrast UV light modulator was made on ZnO grown on an (01{overscore (1)}2) R-plane sapphire substrate. ZnO films are particularly promising for UV photodetectors due to their wide and direct bandgap and large photoresponse. It has been shown that with high quality epitaxial ZnO film, such detectors can achieve high speed operation. Recently, a ZnO p-n diode fabricated using excimer-laser doping has been reported, which makes ZnO promising in other broad device applications, such as Light-Emitting Diodes (LED) and lasers.
In the past, several different metals have been used as a contact metal on ZnO films. For example, epitaxial ZnO film based metal-semiconductor-metal (MSM) device structures have been fabricated using aluminum as the ohmic contact metal (see Ying Liu, C. R. Gorla, S. Liang, N. Emanetoglu, Y. Lu, “J. Electron. Mater.”, 29, 69 (2000)). The device showed fast photoresponse time (˜1 μs) due to high material quality of the ZnO epilayer. However, Schottky type photodetectors are more attractive due to their high speed and low noise performance. An important characteristic of the Schottky diode is its barrier height or turn-on voltage, sometimes called its knee voltage. Schottky barrier heights were first reported by C. A. Mead (see C. A. Mead, “Phys. Lett.”, 18, 218 (1965)), for various metals' contacts on vacuum cleaved n-ZnO surfaces. It has been reported that silver (Ag) has a comparatively high Schottky barrier height (˜0.62 eV) on the cleaved ZnO surface. R. C. Neville and C. A. Mead (see R. C. Neville and C. A. Mead, “J. Appl. Phys.”, 41, 3795 (1970)) further investigated the surface barrier systems consisting of gold and palladium on chemically prepared bulk ZnO. In 1986, H. Fabricius et al. (see H. Fabricius, T. Skeltnep, and P. Bisgaard, “Appl. Opt.” 25, 2764 (1986)), made Schottky barrier type UV photodiodes using gold (Au) as the contact metal on sputtered ZnO thin films. These diodes suffered from severe recombination due to the poor crystalline quality of the film. These photodiodes exhibited slow operating speed and low quantum efficiency due to a large amount of recombination centers in the polycrystalline ZnO layers. Currently, it is believed that no Schottky type of photodetector has been fabricated on ZnO epitaxial films. There is a need for a metal-ZnO Schottky contact which does not suffer from the deficiencies of the prior contacts and which exhibits the advantages mentioned above for broad device applications. It is believed that no Schottky type of photodetector has been fabricated on ZnO epitaxial films prior to this invention.
In accordance with the present invention, there is provided a fundamental semiconductor device structure and process technology having ZnO and MgxZn1-xO films epitaxially grown on an (01{overscore (1)}2) R-plane sapphire substrate and a Schottky diode fabricated with silver as a metal contact on the surface of ZnO and MgxZn1-xO films.
Referring to
An example of a useful means for MOCVD is described in the U.S. patent application Ser. No. 09/905,191 filed Jul. 13, 2001. For example, the MOCVD system is used with a rotating disc reactor chamber. ZnO epitaxial films are grown using DEZn as the zinc precursor and oxygen as the oxidizer. The gas phase reaction between DEZn and oxygen can occur at room temperature and results in particulate formation, which degrades ZnO film properties, including surface morphology and crystallinity. In order to minimize the gas phase reaction, the MOCVD reactor is designed to have a flow-top configuration with high argon push flow. DEZn and oxygen are introduced into the reactor separately. The substrate is rotated at a high speed for improving the thickness uniformity. A 5000-6000 A thick ZnO epilayer was grown with a carrier concentration of about 1016 cm−3.
Referring to
The choice of the metal scheme is also the critical issue for Schottky contact. In the case of ZnO, metals such as Al, which react strongly with chalcogenides (O in ZnO), are expected to produce the most dissociated cations (Zn in ZnO), thus leading to low n-type barrier heights. In comparison, relatively less reactive metals, such as Ag, form higher barriers.
In the present invention, Ag (200 nm) and Al (200 nm) were deposited via electron beam evaporation to form Schottky and ohmic contacts, respectively. The semiconductor Schottky diodes may preferably have circular patterns, where the inner circle is the Schottky contact with a diameter of desirably about 150 μm, and the outside ring is the ohmic contact having a diameter desirably of about 320 μm. The gaps between Schottky and ohmic contacts vary from about 2 μm to about 16 μm. Silver Schottky contact patterns are fabricated using standard photolithography lift-off technique, while the Al ohmic contact patterns are formed using photolithography followed by wet chemical etching. For the Schottky contact, a thick Au layer was finally deposited on the top of the Ag layer, to act as an oxide-resistant layer. It is well known that in fabrication of Schottky contacts, the surface states, contaminants and defects of the semiconductor surface layer affect the barrier height and leakage current.
Referring to
where I is the current, I0 is the saturation current, V is the voltage, □ is the ideality factor, R the series resistance, K the Boltzmann's constant, and T the absolute temperature. The saturation current, I0, is given by:
where A* is the effective Richardson constant, S the Schottky contact area, and □B the barrier height. If the effective Richardson constant, A*, is known, such as in case of GaAs and Si, the barrier height, □B, can be deduced from Eq. (2). However, for ZnO, to the best of our knowledge, an experimental value of A* has not been reported. Thus the barrier height □B can only be calculated using an estimated value of A*. In this work, the barrier height is estimated to be 0.83 eV using the effective Richardson constant A*=32 Acm−2K−2 (A*=4□qm*k2h−3, where m*˜0.27 m017).
The capacitance-voltage (C-V) characteristics of an Ag—ZnO Schottky diode with an electrode gap of 8 μm in a circular pattern are shown in
where □ is the ideality factor, NC the effective density of states in the conduction band, and ND the donor concentration. At room temperature, theoretical value of NC is calculated to be 3.5×1018 cm−3 for ZnO. The flat band barrier height is then determined to be 0.89 eV using Eq. (3).
The capacitance-voltage C-V measurements were performed at 100 kHz and 1 MHz. The Schottky barrier height is determined from:
where the permittivity, □ for ZnO is 9.0□0, S is the Schottky contact area, and Vbi the built-in potential. The barrier height is obtained from:
Shown in
Further, experiments are performed with UV photodetectors designed and fabricated using circular and interdigital (IDT) metal-semiconductor-metal (MSM) structures. Aluminum (Al) and silver (Ag) are used to form ohmic and Schottky contacts, respectively. The Ag—ZnO—Al circular structures are used for Schottky diode studies, while the Ag—ZnO—Ag structures served as Schottky type MSM photodetectors. The thickness of Ag layer is preferably 2000 Å. For the Schottky contact, a 500 Å thick Au layer was finally deposited on the top of the Ag layer, to act as an oxide-resistant layer.
Photoresponse measurements were performed using an Oriel optical system. A Xe-arc lamp and monochromator combination provided the light source. The photoresponse speed of the detector was also measured. The optical excitation source was the 337.1 nm line of a N2 pulse laser, with a pulse width of 2 ns at a repetition rate of 40 Hz. Neutral density filters were used to control the optical power on the detector. Optical energy on the detector was about 10 nJ per pulse. The signal from a 50□ (ohms)-load resistor was reported by a digital scope with a time resolution better than about 1 ns. The bias voltage was about 9V.
Shown in
The Ag—ZnO—Ag MSM structure with IDT configuration such as shown in
The spectra-photoresponse of the Ag—ZnO—Ag Schottky photodetector with an IDT structure is shown in
Finally,
It is clear that the present invention demonstrates fabrication of Schottky diodes on ZnO epitaxial films grown on R-plane sapphire substrate using Ag as a Schottky contact metal. The Schottky barrier height was determined to be 0.85-0.90 eV measured using the I-V-T and C-V methods. Similarly, several experiments were performed with Schottky type UV photodetectors based on ZnO epitaxial films grown on R-plane sapphire substrate Al2O3. Ag was used to form Schottky contact on n-type ZnO. A low frequency photoresponsivity of 1.5 A/W at a bias of 5V was obtained. The leakage current of the device at 5V bias was in the order of 1 nA. The photoresponse of the detector showed a fast component with a rise time of 12 ns, and a fall time of 50 ns.
Although the invention is described herein with reference to ZnO film, it is to be noted that MgxZn1-xO films can be utilized to produce similar results. The direct band-gap of ZnO can be tuned from 3.3 eV to 4.0 eV by alloying ZnO with MgO to form the ternary compound, MgxZn1-xO in the Mg composition range of 0 to 0.34. In comparison, the MgxZn1-xO epitaxial films have shorter wavelength range than the ZnO epitaxial films. (11{overscore (2)}0) MgxZn1-xO epitaxial films are grown on (01{overscore (1)}2) sapphire substrates (R-plane) with different Mg contents. Schottky type photodetectors were fabricated with silver as Schottky metal contacts on surface plane of MgxZn1-xO films. The transmission measurements show that the cut-off wavelength varied with the amount of incorporation of Mg content. These photodetectors showed higher speed and lower leakage current compared to their photoconductive counterparts.
While the invention has been described in related to the preferred embodiments with several examples, it will be understood by those skilled in the art that various changes may be made without deviating from the fundamental nature and scope of the invention as defined in the appended claims.
This application is a continuation of co-pending application Ser. No. 10/158,540 filed on May 30, 2002, which claims priority to Provisional Application Ser, No. 60/344,337 filed on Jan. 4, 2002, the contents of which are incorporated herein by reference.
Number | Date | Country | |
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60344337 | Jan 2002 | US |
Number | Date | Country | |
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Parent | 10158540 | May 2002 | US |
Child | 11042533 | Jan 2005 | US |