Method of making selective conductive regions in diamond layers

Abstract: A diamond lattice substrate is irradiated with a high energy particle of sufficient flux, energy level and time period to irreversibly transform an area of a plane normal to the axis of irradition into conductive graphite. The substrate is cooled during irradiation to confine the graphite to the area of the plane at a desired depth within the substrate.

Description: The present invention relates generally to a method of producing conductive regions in a non-conductive material, and more specifically to forming conductive regions in a diamond lattice substrate. We have been engaged in extensive research in the effect of high energy charge particle bombardment onto diamonds. As a result of this research, we obtained U.S. Patent 4,200,506 directed to the use of high energy particle beams to produce identifying marks in gemstones, specifically diamonds. The highly localized alteration of the optical properties of the diamonds by introduction of very thin layers of radiation damage lattice is described therein. With the advent of the successful growth of diamond films, we have turned our attention to the use of bombardment by high energy particle beams to create conductive graphite areas in diamonds. This application would have a widespread use in semiconductor devices, integrated circuits, miniaturized electrical devices and circuit boards, as well as memory devices. The relative resistance of diamond to radiation, as well as its high thermal conductivity would make it an ideal package, insulating layer, heat sink, etc., as compared to other materials presently being used with semiconductors. Similarly, by using a diamond package, optical communication to the interior of the package may be obtained. In the patent abstract of Japan, Volume 7, number 1, 4, 7 (C-173(1292), 28th June 1983; and JP-A-5860 696 (Rikagaku Kenkyusho) 11-04-1993 an electrically conductive diamond and its preparation by implanting ions, like Ar⁺ is disclosed. This ion implantation produces some crystal damage at the surface of the crystals, but also acts as a dopant to reduce the resistance and increase the conductivity of the diamond material. The crystal damage is almost a second effect compared to the doping effect GB-A-2 072 927 (RCA Corporation) describes an ion implanted diamond video disk stylus. A conductive layer is formed by ion implantation using high energy charged particles such as boron. Those are implanted in the diamond lattice. It has been recognized that there was some damage to the diamond. However, the principle cause of the increased conductivity is because of the doping with the boron. The desireability of forming high conductive regions in insulative material is described in U.S. Patent 4,511,455 to Forrest et al. Low resistivity material is obtained by irradiating carbon-containing materials with particles having atomic weight of at least one. This process involves the chemical break down of carbon-containing compounds by radiolysis caused by the impinging charged particles. The technique creates a cylindrical column of conducting amorphous type carbon. Although being applicable to generic carbon-containing materials, the Forrest et al. patent does not address specifically the properties of diamonds, their use in the electronic industry, and the ability to form conductive regions below the surface of the diamond. Thus, it is an object of the present invention to provide a method of making selective conductive regions in a diamond substrate. Another object of the present invention is to provide a method of making conductive regions in a diamond substrate below the surface of the substrate. A still further object of the present invention is to provide a method of making conductive regions in a diamond substrate which is capable of being used in high-temperature, high-radiation environments. These and other objects of the invention are obtained by irradiating a diamond lattice substrate with a high energy charged particle of sufficient flux, energy level and time period to irreversibly transform an area of a plane normal to the axis of irradiation into conductive graphite. The substrate is cooled during irradiation to confine the graphite to the area of the plane at a desired depth within the substrate. The irradiation is conducted for a period of a few minutes to a few hours, and at energy levels of 100 KeV to 4 MeV. The charged particles are selected from the group of protons, deuterons and alpha particles, although preferably being monoenergetic protons. The cooling is in the range of -269°C to room temperature. The process is capable of producing contacts and interconnects on an integrated circuit for a device or on a circuit board. Similarly, it can form the plates of a capacitor and terminals on a container for electronic devices. It is also capable of forming resistors and other conductive elements through or in an insulative diamond layer. Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagrammatic cross-sectional view of a diamond lattice substrate that has been irradiated; Figure 2 is a diagrammatic magnified view of the diamond lattice substrate of Figure 1; Figure 3 is a cross-sectional view of an integrated circuit having a diamond package layer with conductive terminal therein; Figure 4 is a cross-sectional view of a capacitor and resistor formed in a diamond layer; and Figure 5 is a perspective view with cut away portions showing a circuit board incorporating the principles of the present invention. DETAILED DESCRIPTION OF THE DRAWINGS Referring now to Figure 1, a diamond lattice substrate is illustrated that has been bombarded by a proton beam 2. As the protons enter the crystal through surface 4, they lose energy through ionization. The crystal lattice is not strongly heated and no changes occur in area 6 of the crystal. At the end of the proton particle's path, a change takes place in a very small and localized region off the crystal lattice shown as area 8. The remainder of the crystal is unchanged and shown herein as area 10. Figure 2 shows individual displacement spikes which is the change occurring in the small, localized area due to the intense heat produced wren the proton particle stops. Each spike as shown may comprise an area of about 0.01 micrometers in diameter and involve about 10⁴ atoms. The area in which the displacement spikes are developed constitutes a permanent change that is detectable upon microscopic examination. When natural diamond crystals are irradiated with monoenergetic protons from a Van de Graaff accelerator, permanent changes take place in the crystals at the point where the particles come to rest. If particle energies in the range from about 0.1 MeV to about 4 MeV are used, the crystal surface will not be damaged by sputtering nor will nuclear reactions occur which would render the diamond radioactive after completion of the treatment. The protons with which the diamond is bombarded will penetrate the crystal in a well defined and highly predictable manner stopping at a depth of a few micrometers to several tens of micrometers depending upon their initial energies. Energy levels in the range of about 0.7 MeV to 2 MeV are preferred. When the particles enter the crystals they first lose energy through ionization and the crystal lattice is not strongly heated. However, at the end of the particle's path a detectable change in the crystal lattice takes place in a very small and localized region. This region is characterized by the development of displacement spikes which result from the intense localized heating caused when the particle stops at the end of its path through the crystal. The zone in which the displacement spikes are developed constitutes a permanent change which is visible upon microscopic examination. Cooling the crystal during irradiation keeps the bulk temperature low so that the structural changes occurring by the displacement spike is confined to a clearly defined zone. By maintaining the temperature in the range from room temperature to liquid helium temperature the desired effect is achieved. The temperature selected is a function of the energy level of particles and the desired thickness of the changed area. The lattice change in the stopping region causes the previously highly resistive or insulative portion of the crystals to becomes a lower resistance, conductive polymorph of carbon, namely graphite. The lateral extent of the pattern is defined by known masking techniques. The depth of penetration of the protons into the crystal lattice is directly proportional to the energy level employed. Accordingly, it is possible to produce altered lattices at different depths below the crystal surface. Single crystals of natural diamond were irradiated with protons ranging in energy from 0.7 MeV to 1.8 MeV. The particle beam was supplied by a Van de Graaff accelerator. Approximately 10¹⁶ particles per hour per cm² were incident upon the crystal with an average beam current of 1.5 microamperes. All irradiations were performed with a defocused beam so that the proton intensity distribution across the beam was as uniform as possible to eliminate formation of hot spots. High particles fluxes were avoided to prevent excessive heating of the target and it was cooled to liquid nitrogen temperature (-196 °C) during the irradiations. The duration of the irradiations ranged from a few minutes to several hours. The formation or a thin dark layer is very pronounced after irradiating for 30 minutes. Under these conditions of irradiation, the actual dimensions were approximately as follows: Average thickness of the crystal: 1 to 2 mm. Depth off the altered layer below the crystal surface: roughly 15 microns. Thickness of the altered layer: approximately 1 micron or less. The resistance of the diamond has been measured as greater than 250 mega ohms and the resistance of the altered layer has been measured as less than 500 ohms. This represents an increase in conductivity by a factor or more than 10⁵. The method of measuring is as follows: Electrical contacts are placed against the diamond surfaces and across the conductive layers. This technique may be used with electrical, electronic and integrated circuits. As illustrated in Figure 3, an integrated circuit 20 having a collector region 22, a base region 24 therein and an emitter region 26. The semiconductor circuit 20 is divided into islands by, for example, a dielectric lateral isolation regions 28. The bottom of the substrate includes a diamond insulative layer 30 and the top includes a diamond insulative layer 32. The present method is used to form a conductive graphite contact region 34 extending through the bottom insulative diamond lattice 30 to the collector region 22. The structure in Figure 3 may be later mounted into a packaging, or the regions 30 and 32 may represent the packaging. Thus, the graphite region 34 would be considered a terminal on the packaging. A specific use of the electronic device illustrated in Figure 3 would be an optical semiconductor device since the diamond layers 30 and 32 are optical transmitters. Thus, the device can be a light emitting diode or a photosensor. The use off the diamond layers 30 and 32 and the process of the present invention provides the ability to use the diamond layers and a method of forming electrical contacts to a semiconductor and integrated circuit within the package while allowing optical transmission. The diamond layers 30 and 32 are also very resistant to radiation and provide good thermal conductivity. This removes the need for having heat sinks separate from the insulative layer, which in this case is the diamond layers 30 and 32. The method described above is carried out at varying levels of energy to produce the three-dimensional contact 34. The present process can also be used to form electrical devices as illustrated in Figure 4. The process is used in a diamond layer or substrate 40 to form capacitor plates 42 and 44 separated from each other by the unaltered diamond lattice. Conductor contact region 46 extends from the top plate 42 to the surface of the diamond substrate 40 and a resistive region 48 is formed in the diamond lattice using the method of the present invention. The present process may also be used to form circuit boards which because they are formed of diamonds are capable of high heat environments. A diamond lattice circuit board 50 is illustrated in Figure 5 as having a top conductor pattern 52 formed therein with a via or pass through conductive layer 54 connecting the top layer 52 to a bottom conductive pattern 56. The method of the present invention is used to form the top and bottom conductors 52 and 56, as well as the pass through or via 54. The conductivity or resistivity of the individual graphite layers is a function of the amount of graphite lattice per unit area as well as the depth or cross-sectional area. The lateral restriction of the pattern is accomplished by well known masking methods using metal templates or by systems which are capable of transmitting a fine beam and moving it laterally. As discussed above, the depth or location of the conductive region within the body of the diamond crystal lattice is a function of the energy of the high energy particle beam, as well as the cooling step to confine it to a given plane. With the advent of optical transmission for use in memory and microprocessors, the use of optically transparent diamonds and the ability to form conductors therein will become very useful. From the preceding description of the preferred embodiments, it is evident that the objects of the invention are attained, and although the invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation.

Claims: A method of making and using conductive regions in a diamond lattice substrate comprising: providing a diamond lattice substrate; and selectively irradiating portions of said diamond lattice with high energy charged particles to irreversibly transform portions into zones of conductive graphite below the surface of the diamond substrate and electrical contact points on the surface of the diamond substrate. A method according to Claim 1, including cooling said substrate during irradiation to confine said graphite to areas at desired depths within said substrate. A method according to Claim 2, wherein said substrate is cooled to a range of 17°C to -269°C. A method according to Claim 1, wherein said irradiation is for a period in the range of a minute to several hours. A method according to Claim 1, wherein said high energy charged particle is selected from the group of protons, deuterons and alpha particles. A method according to Claim 1, wherein said particles are monoenergetic protons. A method according to Claim 1, wherein said irradiation is at an energy in the range of 0,1 MeV to 4 MeV.

Inventors: DRESCHHOFF GISELA A M, ZELLER EDWARD J, DRESCHHOFF, GISELA A. M., ZELLER, EDWARD J.
Applicants: DRESCHHOFF GISELA A M, ZELLER EDWARD J, DRESCHHOFF, GISELA A. M., ZELLER, EDWARD J.
Application year: 1990
Main classification: C30B33
IPC codes: H01L21, B01J19, H01G4, H01B1, H05K3, C04B41