Abstract:
A high dielectric insulator for integrated circuit use is produced by depositing hafnium on a silicon dioxide surface of a silicon wafer and then promoting a solid-state reaction between the silicon dioxide and the hafnium by heating the wafer to produce hafnium silicate.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
     BACKGROUND OF THE INVENTION 
     The present invention relates to integrated circuit fabrication techniques and specifically to a method of producing an insulating layer on an integrated circuit for structures such as insulated gate field effect transistors (IGFET). 
     Integrated circuits produced on silicon wafers make use of silicon dioxide (SiO 2 ) as an insulator between conductors including interconnections between circuit elements, capacitor plates, and the gate contact and the current carrying channel (the “transistor channel”) separating drain and source contacts. 
     With the continued miniaturization of circuit elements in ultra-large scale integrated (ULSI circuits), the thickness of the SiO 2  layer that forms the insulator in an IGFET must be decreased so as to offset the reduction in area of the gate contact while preserving the necessary capacitive coupling. Although improvements in SiO 2  processing have allowed high quality SiO 2  layers of the required thickness to be produced to date, a fundamental thickness limitation looms for gate oxides thinner than approximately 12 Å. At this thickness, electron tunneling is expected to provide current leakage that is unacceptably high even for high performance devices and much too high for increasingly popular low power devices. 
     Electron tunneling could be prevented if a material having a higher dielectric constant (κ) than SiO 2  could be found to serve as the insulation on the gate. With such a high κ insulator, the gate insulation could be made physically thicker for a given capacitance dramatically reducing the tunneling. 
     Potential materials for producing a high κ electrical insulator must produce an electrical interface with the silicon having few fixed charges or recombination centers to not limit carrier mobility in the transistor channel. The material should readily adopt an amorphous phase to reduce electrical leakage and doping diffusion along grain boundaries. Further, the material must not be prone to reactions with the silicon substrate that would cause formation of an interfacial SiO 2  layer. This latter interfacial SiO 2  layer acts to reduce the capacitance of the high κ material by adding a small series capacitance lowering the overall capacitance according to standard series additions of capacitance. 
     Zirconium (Zr) and hafnium (Hf) compounds have been investigated as high κ materials for integrated circuit application. Oxides of both elements have high dielectric constants (approximately 25) and can form stable silicate phases (MSi x O y ) M═Hf or Zr) and appear to be stable in contact with silicon at temperatures approaching required integrated circuit processing temperatures. It appears that a relatively small amount of Hf or Zr can significantly increase dielectric constants and that deleterious hafnium-silicon or zirconium-silicon bonds will be energetically unfavorable compared to silicon-oxygen bonds at the interface to the silicon substrate. 
     Previous attempts to grow hafnium-silicate or hafnium-oxide have used electron beam evaporation of hafnium-silicate onto a bare silicon substrate, sputter deposition of hafnium-silicate onto a bare silicon substrate, or chemical vapor deposition (CVD) of hafnium-oxide or hafnium-silicate on bare silicon substrate. 
     BRIEF SUMMARY OF THE INVENTION 
     The electrical and mechanical qualities of the silicon-SiO 2  interface are extremely important in the production of semiconductor devices. The present inventors believe that removing the SiO 2  layer from the silicon substrate, required in the prior art deposition of hafnium silicate, may result in contamination of the silicon surface, especially in the moderate vacuum levels found in deposition chambers or CVD reactors. This contamination can result in an unwanted, thin SiO 2  layer and/or a poor quality silicate layer. 
     Accordingly, the present invention creates a hafnium-silicate layer without removal of the SiO 2  layer, depositing hafnium directly on the SiO 2  layer then heating the substrate to promote a solid state reaction producing hafnium-silicate and consuming the underlying SiO 2 . 
     Specifically, the present invention provides a method for the manufacture of hafnium-silicate film including the steps of depositing hafnium on the silicon dioxide layer of a silicate substrate and heating the substrate to react the deposited hafnium with the silicon dioxide layer to form a corresponding layer of hafnium-silicate. 
     Thus, it is one object of the invention to provide a method of producing a hafnium-silicate layer that does not require removal of a protecting silicon dioxide layer from the substrate. 
     The reaction step may continue until the silicon dioxide-between the hafnium-silicate and the silicon substrate is substantially removed or the hafnium has fully reacted with all silicon dioxide between the hafnium-silicate and the silicon substrate. 
     Thus, it is another object of the invention to provide method of producing a hafnium-silicate layer that is in direct contact with the silicon without an intervening and capacitance-decreasing layer of silicon dioxide. 
     The deposition of hafnium may be performed by electron beam evaporation. 
     Thus, it is another object of the invention to provide a method of depositing hafnium on the silicon dioxide that avoids the ion damage, for example, attendant to sputter deposition. 
     The foregoing and other objects and advantages of the invention will appear from the following description. In this description, reference is made to the accompanying drawings, which form a part hereof, and in which there is shown by way of illustration, a preferred embodiment of the invention. Such embodiment and its particular objects and advantages do not define the scope of the invention, however, and reference must be made therefore to the claims for interpreting the scope of the invention. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a simplified schematic representation of a vacuum chamber suitable for practicing the present invention showing an electron beam evaporator positioned near a substrate that may be heated by a substrate-heating unit; 
     FIG. 2 is a flow chart of the steps of the present invention; 
     FIG. 3 is a simplified, fragmentary cross-section of the substrate of FIG. 1 before a first cleaning step of the flow chart of FIG. 2; 
     FIG. 4 is a figure similar to that of FIG. 3 showing deposition of metallic hafnium on the surface of the substrate; 
     FIG. 5 is a figure similar to that of FIGS. 3 and 4 showing the formation of the hafnium silicate layer after heating the substrate of FIG. 4; and 
     FIG. 6 is simplified, fragmentary cross-section of a substrate showing construction of an insulating gate field effect transistor using the present invention. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     Referring now to FIG. 1, a reaction chamber  10  provides a vacuum vessel  12  suitable for producing an ultra high vacuum by means of a multistage vacuum pump  14 . A vacuum gauge  17  allows control of the vacuum within the region of the vacuum vessel  12  for a predetermined setting. 
     Positioned within the vacuum vessel  12  is a wafer carrier  16  holding a silicon wafer  18 . The wafer carrier  16  includes leads  20  connected to heater control  22  to provide for resistive heating of the silicon wafer  18 . An optical pyrometer  23  or similar device may monitor that heating to control the temperature precisely. 
     An electron gun  24 , opening into the vacuum vessel  12 , produces an electron beam  26  directed against a hafnium target  28  to create a beam of hafnium  30  directed toward an upper surface of the silicon wafer  18 . Electron beam evaporators of this type are described by B. T. Jonker in the  Journal of Vacuum Science Technology  A8, 3883 (1990). 
     Referring now to FIGS. 2 and 3, at a first process step  31 , a silicon wafer  18  is inserted into the wafer carrier  16 . As shown in FIG. 3, the silicon wafer  18  includes a polysilicon layer  33  lying under a silicon dioxide layer  34 . The silicon wafer  18  is preferably a commercial Si wafer with doping levels appropriate for eventual device fabrication, and has a high-quality oxide layer (approximately 15 Å thick). Upon receipt of the silicon wafer  18 , a layer of surface contamination  36  may be present, for example, of oils or other dirt providing a carbon contamination. 
     At the process step  31 , the silicon wafer  18  is heated by the current through leads  20  to approximately 500° C. rendering a surface nearly free of carbon contamination. Volatile carbon  37  is extracted by the vacuum pump  14 . 
     At a next process step  32 , the silicon wafer  18  is cooled to room temperature and a sub-monolayer to monolayer of 99.9% pure hafnium (excluding approximately 3% zirconium) is deposited on the silicon wafer  18  using the electron beam evaporator (comprised of electron gun  24  and target  28 ). 
     Referring to FIG. 4, the hafnium layer  38  is deposited directly on the silicon dioxide layer  34 . A restricted region of hafnium deposition may be obtained by masking and etching techniques well known in the art. 
     Referring to FIGS. 2 and 5 at succeeding process step  40 , the silicon wafer  18  having the hafnium layer  38  is annealed at one or more annealing steps of increasing temperature up to 800° C. but within a range of 750 to 850° C. Each annealing step includes heating and cooling of the silicon wafer. The annealing causes the hafnium layer  38  to form stable silicate phases HfSi x O y  fully consuming the SiO 2  between the deposited hafnium layer  38  and the polysilicon layer  33 . 
     Complete reaction of the hafnium silicate layer  42  may be monitored x-ray photoelectron spectroscopy (XPS) either concurrently with the step  40  or periodically between repetitions of the step  40  at increased annealing temperatures. Specifically, the spectrum obtained by the XPS at process step  40  may be compared against spectra obtained from samples of hafnium compounds formed by electron beam evaporation of thicker films that are subsequently processed to create HfSiO 2 , HfO 2 , and HfSi x O y  as reference spectra. Generally, upon annealing to progressively higher temperatures, the hafnium spectral feature sharpens and the centroid of the peak shifts approximately 0.7 eV to deeper binding energies while beginning to conform to a doublet characteristic of the silicate. When the annealing has been completed, the hafnium features of the XPS spectra of the silicon wafer  18  should match that of the bulk silicate material. 
     It is believed that the hafnium silicate layer  42  when fully reacted produces an amorphous film that is thermally stable in vacuum to temperatures in excess of 800° C. The inventors have found compelling evidence that the silicate substrate interface is stable against the formation of a silicon dioxide layer beneath the hafnium silicate layer  42 . 
     An additional step after step  40  (not shown) may include full oxidization of the hafnium silicate layer  42  through rapid thermal annealing. 
     Referring now to FIG. 6, an insulated gate field effect transistor  50  may be produced by doping a transistor channel  52  of the silicon layer  33  according to techniques well known in the art and then growing a hafnium silicate layer  42  on top of the transistor channel  52  as described above. A conductive gate pad  54  may then be deposited on top of the hafnium silicate layer  42  to provide for a gate contact and the oxide  34  on either side of the hafnium silicate layer  42  removed to allow a source and drain contact  56  to be placed in contact with the transistor channel  52 . The hafnium silicate layer  42  replaces the silicon dioxide layer traditionally used in such devices. 
     The hafnium silicate layer  42  may also be useful in the production of other circuit elements in integrated circuits where high dielectric material is used and smaller feature size is desired. 
     The present method provides a number of advantages over direct deposition of silicates. The first is that it allows well-developed procedures for producing a high quality silicon oxide layer on the silicon substrate to be used, ensuring a good silicon-silicon dioxide interface as has been described above. Furthermore, it appears that high quality hafnium silicate cannot be deposited directly on a silicon substrate using electron beam evaporation because such direct deposition promotes deleterious hafnium-silicon bonding. 
     It is specifically intended that the present invention not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.