Abstract:
A method for making diamond material comprises providing a deposition chamber; placing a substrate in said deposition chamber; sealing and evacuating said deposition chamber; admitting to said deposition chamber gases suitable for diamond deposition; heating said substrate to a diamond deposition temperature; igniting and maintaining a plasma adjacent to a growth surface of said substrate such that said plasma extends no further than 1 mm from said growth surface of said substrate; and maintaining said plasma during a diamond deposition time period.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to methods for synthesizing synthetic diamond materials and diamond material produced thereby. More-particularly, the present invention relates to methods for synthesizing high-efficiency diamond and material and diamond material produced thereby. 
     2. The Prior Art 
     It has long been known that diamond is an ideal potential candidate for heat transfer applications such as described above. Diamond, both natural and synthetic, is known in the art to exhibit thermal conductivity superior to all other known materials. Diamond manufactured by chemical vapor deposition, a modern and widely studied means of diamond synthesis, has been shown to exhibit thermal conductivity in excess of 20 W/cm/° C. At the same time, diamond&#39;s thermal expansion coefficient is approximately 1 to 1.7×10 −6 /° C. over the operating temperature range of silicon-based microprocessors. Finally, diamond has the highest Young&#39;s modulus, or stiffness, of any known material, excluding unidirectional module of certain fibers not applicable to the present invention. The combination of these properties is unique to diamond. 
     It has not been previously possible, however, to provide diamond material for use in such applications at a price that permits their commercial use. Integrated circuits such as microprocessors are fabricated on integrated circuit dice having areas of 1 square centimeter or larger. Use of diamond material for heat transfer from such devices having areas as large as 1 square centimeter or larger has been, at best, a laboratory curiosity because of the prohibitively high expense of providing the diamond material. 
     Diamond synthesis through chemical vapor deposition (CVD) is by now a well-established art. Commercial diamond deposition systems are available and products employing CVD diamond are routinely sold for commercial applications ranging from cutting tools to heat spreaders. 
     All diamond CVD processes to date have been characterized by very low process efficiency in terms of the amount of diamond produced in response to consumption of energy and synthesis materials. There has been a long-felt need within the CVD diamond industry to improve diamond CVD process efficiencies. This long felt need has given rise to vigorous prior but unsuccessful efforts to achieve significantly higher process efficiencies. 
     Diamond chemical vapor deposition is accomplished by energizing an appropriate gas mixture (most commonly containing a preponderance of hydrogen and a minor hydrocarbon constituent, the latter being the source of carbon which is deposited as diamond) in a suitable deposition reactor and providing means for the diamond precursor chemical specie(s) generated by said application of energy to encounter a surface whose temperature, chemistry, and surface preparation properties permit the nucleation and growth of diamond layers in a manner well-known to those skilled in the art. 
     It is thought, and there is considerable supporting and little contradicting evidence, that a key step in the formation of diamond through the majority of useful diamond CVD processes is the dissociation of ordinary molecular hydrogen gas to form atomic hydrogen. Once formed, this species effects several actions known to be required for diamond CVD to occur at useful rates: it stabilizes carbon in the sp 3  (diamond) bonding configuration and forestalls the formation of undesirable sp 2  (graphitic) bonds; it abstracts hydrogen from hydrocarbon precursor species and thereby makes carbon available for incorporation in the growing diamond lattice; and it selectively reacts with, and returns to the gas phase, those small graphitic domains which may from time to time appear during the diamond CVD process, thereby preventing the formation of graphite-contaminated diamond which would be of no significant utility. 
     While the details of surface chemistry underlying diamond CVD remain to some degree obscure, it is widely observed that the successful synthesis of diamond through most CVD methods requires production of atomic hydrogen. The economics of diamond CVD processes are essentially the economics of generating atomic hydrogen. 
     A few instances of diamond CVD requiring little or no atomic hydrogen are known to the art. A laser-driven diamond CVD process developed by QQC, Inc., appears not to require hydrogen in its precursor atmosphere. Similarly, diamond CVD using microwave-assisted plasmas has been accomplished under conditions of reduced hydrogen concentration. While these results suggest subtleties to diamond CVD chemistry that remain to be elucidated, they confirm the fundamental scheme in which a gas, or mixture of gases, is energized by a variety of modalities to effect diamond CVD under appropriate conditions as specifically required by the circumstances chosen by the practitioner of the art. To date, none of the low-hydrogen diamond CVD processes has demonstrated commercial utility. 
     In all known diamond CVD processes having commercial utility, production of atomic hydrogen is required and is the primary energy-consuming step in those processes. The costs of producing atomic hydrogen in large quantities are considerable, and include the direct cost of energy as well as the cost of equipment needed to apply that energy in a useful manner. As will be seen, the diamond CVD processes that constitute the current art are extremely inefficient, leading to very high energy and equipment costs. 
     The heart of diamond CVD process inefficiency lies in the short lifetime of the atomic hydrogen species and in the energy cost of creating that species. Atomic hydrogen is thermodynamically driven to recombine to form molecular hydrogen, which plays no significant role in diamond CVD. The recombination, or loss, of atomic hydrogen proceeds very rapidly on surfaces and comparatively slowly in the gas phase. This relationship arises because recombination of two hydrogen atoms requires a release of energy in order to proceed. In the gas phase, quantum mechanical effects prohibit the release of the recombination energy when only two hydrogen atoms collide. Thus, gas-phase recombination of atomic hydrogen requires simultaneous collision of at least three bodies, two of which are hydrogen atoms. The third body, which may be another hydrogen atom, molecule, or non-hydrogen molecule, dissipates the recombination energy as kinetic energy. 
     On surfaces, the required kinetic energy dissipation pathway is provided by the surface itself. The recombination of atomic hydrogen on surfaces is a two-body collision because of this, and it proceeds very rapidly compared to gas phase recombination. The recombination energy appears as heat in the substrate. Much of the substrate heating observed in diamond deposition arises from the energy of atomic hydrogen recombination. 
     Because the manufacture of atomic hydrogen requires substantial energy, and because the species, once made, is continuously and rapidly destroyed by recombination with itself and with other molecular species, successful diamond CVD requires manufacture of enormous amounts of atomic hydrogen compared with the amounts which actually participate in diamond deposition. This is the root of the inefficiency of current diamond CVD art. 
     A common feature of nearly all diamond CVD processes is the manufacture of atomic hydrogen at distances relatively remote from the deposition region. Thus, microwave diamond CVD entails the formation of microwave plasma regions, the main bulk of which do not contact the deposition surface and which may be several inches away from that surface. This provides ample opportunity for loss of valuable atomic hydrogen through recombination. 
     Similarly, diamond CVD practiced with heated filaments suffers from relative inefficiency of atomic hydrogen production (due to limits on filament temperature) as well as losses due to the inability to locate filaments in immediate proximity to the deposition surface, which limitation arises from substrate overheating due to radiation of energy from the filament. 
     A third common means of diamond CVD, use of electrically-driven plasma torches which manufacture atomic hydrogen principally through superheating a stream of molecular hydrogen, must transport manufactured atomic hydrogen in a supersonic stream from the energy application point to the deposition region, which is typically at least several inches away. Much atomic hydrogen is lost, but because the supersonic gas stream impacts the substrate at high velocity, stagnation boundary layers are thin, and the diffusive flux of atomic-hydrogen to the surface is relatively large, giving high growth rates for this method. Overall efficiency, however, remains poor, because of the enormous overproduction of atomic hydrogen inherent in the process compared with the small fraction that reaches the growth surface. 
     Diamond CVD growth efficiency is often expressed in terms of the weight of diamond formed per unit time as a function of the amount of power supplied to the system. While this figure of merit ignores the consumption of precursor gases, it is a useful index of the energy efficiency of a diamond CVD process and makes possible an efficiency comparison among different diamond CVD processes. A more comprehensive index of diamond growth efficiency will be presented below. 
     As reported (MRS Bulletin, September 1998, volume 23, no. 9, pp 22-27, in particular FIG. 3 on page 24), the best diamond CVD processes have reached a power efficiency of approximately 6.25 kilowatts (kW) per hour per carat of diamond deposited. A carat is equal to 0.2 grams. As reported in this reference, this efficiency level has been reached by application of successively greater amounts of power to the growth system, reaching up to 200 kW in some systems. 
     Unfortunately, the capital cost of equipment capable of sustaining such extremely energetic processes is large. Thus, the modest increase in deposition efficiency gained by use of more power is offset by the resultant economic penalty. The net result of this technology development pathway has been an increase in diamond deposition rate without significant decrease in deposition cost. Breakout from the constrained high cost of diamond synthesis has been a long-sought goal in the art. 
     A more useful diamond CVD growth efficiency index should account for consumption of gases as well as energy use. In the same manner that energy consumption can be expressed in terms of kilowatt-hours per carat of diamond produced, hydrogen and methane consumption can be expressed in terms of standard liters per carat of diamond produced. If gas consumption in standard liters of hydrogen and methane per carat of diamond produced is added to electrical power consumption in kilowatt-hours per carat of diamond produced, and the inverse of that sum is computed, an index results that correctly reflects diamond CVD process efficiency by varying inversely with energy and gas consumption rates. This index, referred to herein as the “raw composite growth efficiency” makes it possible to compare the growth efficiencies of disparate diamond CVD processes. 
     Process efficiencies for the principal means of diamond CVD are shown in Table 1. The data have been compiled from literature reports and from experience with each of the listed modalities. Energy efficiency is expressed in terms of kW-Hr/carat of diamond produced, while raw material consumption is expressed as liters of gas consumed per carat of diamond produced. Raw composite growth and normalized composite growth efficiencies are calculated as stated above, and are presented with the efficiency of the arc jet modality normalized to 100%. 
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Comparative Diamond CVD Process Efficiencies 
               
             
          
           
               
                   
                   
                 Hot  
                   
                 Current 
               
               
                   
                 Arc Jet 
                 Filament 
                 Microwave 
                 Invention 
               
               
                   
               
             
          
           
               
                 Power  
                 6.8 
                 44.6 
                 34.1 
                 2.1 
               
               
                 consumption, 
               
               
                 KW-Hr/carat 
               
               
                 Hydrogen 
                 2,048 
                 669 
                 546 
                 86 
               
               
                 consumption, 
               
               
                 standard 
               
               
                 liters/carat 
               
               
                 Methane 
                 102.4 
                 33.4 
                 27.3 
                 4.3 
               
               
                 consumption, 
               
               
                 standard 
               
               
                 liters/carat 
               
               
                 Raw composite 
                 0.00046 
                 0.00134 
                 0.00165 
                 0.00792 
               
               
                 growth 
                 4 
               
               
                 efficiency 
               
               
                 Normalized 
                 100% 
                 289% 
                 355% 
                 1,700% 
               
               
                 composite 
               
               
                 growth 
               
               
                 Efficiency 
               
               
                   
               
             
          
         
       
     
     The foregoing table discloses the relative growth efficiencies of diamond CVD methods, including that achieved by this invention. No diamond deposition method, other than this invention, is known to produce diamond at a raw composite growth efficiency greater than approximately 0.00165 as computed according to the method shown above. These growth efficiencies are understood to be in reference to CVD diamond material of commercially useful purity. One means of establishing purity of a CVD diamond material, and a means commonly employed in the art, is through use of Raman spectroscopy. So measured, the Raman signature of commercially useful CVD diamond shows an sp 3  (diamond-bonded carbon) peak having a full width at half maximum value of 12 wavenumbers or less, and exhibits non-sp 3  features of intensity less than 50% of the sp 3  peak intensity in the wavenumber region from 1200 cm −1  to 1700 cm −1 . 
     BRIEF DESCRIPTION OF THE INVENTION 
     According to one embodiment of a method according to the present invention, atomic hydrogen and other requisite diamond deposition species are generated in intimate proximity to the deposition surface, thereby greatly reducing the amount of atomic hydrogen and other precursors lost to the process, and concurrently greatly reducing the amount of energy and precursor material required to achieve a given diamond deposition rate. 
     According to another embodiment of a method according to the present invention, atomic hydrogen and other requisite diamond deposition species are generated at pressures greater than 20 Torr using plasmas excited at powered electrodes from energies at frequencies greater than 50 MHz. 
     The diamond material employed in the present invention is deposited using a process having greatly enhanced growth efficiency and is thus cost effective to employ for the purposes set forth herein. Diamond materials employed in the present invention are referred to herein as “high-efficiency” diamond materials. That term, as used herein, shall be used to identify diamond material having a composite growth efficiency greater than about 0.003. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING FIGURES 
     FIG. 1 is a schematic representation of a first exemplary process according to the present invention for synthesizing high-efficiency diamond material. 
     FIG. 2 is a schematic representation of a second exemplary process according to the present invention for synthesizing high-efficiency diamond material. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Those of ordinary skill in the art will realize that the following description of the present invention is illustrative only and not in any way limiting. Other embodiments of the invention will readily suggest themselves to such skilled persons. 
     Referring now to FIG. 1, a schematic representation illustrates a first actual exemplary process according to the present invention for synthesizing high-efficiency diamond material for use in the present invention. 
     Specifically, the process illustrated in FIG. 1 employs a chamber  10  affording a controlled atmosphere and pressure, wherein is disposed a substrate support  12  for supporting a substrate  14  on which it is desired to deposit diamond. A heat source  16  and temperature measurement and control system  18  are employed whereby the temperature of the deposition substrate may be controlled within a range known to those skilled in the art to support diamond growth. A signal source  20  generates energy in the form of alternating current having a frequency greater than approximately 50 MHz may be applied to the substrate support structure in such a way as to cause a high electric field to appear at the deposition substrate surface in order to cause the electrical breakdown of gases immediately adjacent to that surface with the formation of a plasma near the deposition substrate surface. 
     More specifically, an actual embodiment of this invention employs a metallic rod  22  suitable for the conduction of electrical energy at 400 MHz. The rod is fixed at its base through an electrically nonconductive support  24  that provides mechanical stability and allows the structure to be energized with 400 MHz energy. The rod is approximately 6 inches in overall length and is oriented substantially vertically, although this orientation is not critical to the operation of methods according to the present invention. At the unfixed end of the rod, a disc having a diameter of approximately 1 inch and a thickness of approximately ⅛″ is attached to the rod to form substrate support  12  at the end of the rod suitable for the support of a silicon wafer or other suitable substrate on which it is desired to grow a diamond coating. This disc and rod are fabricated from materials compatible with the environment required for diamond deposition as is known in the art. Molybdenum is a suitable material among others known in the art. 
     As shown in FIG. 1, energy at 400 MHz is admitted into the deposition chamber and applied to the base of the above-described rod/support structure such that the rod  22  and support  12  form an electrical quarter-wave component well-known to those skilled in the art and designated herein as the powered electrode. A characteristic of such a structure when energized in the manner described is the appearance of high electrical fields at the end of the structure distant from the end at which the energy is applied. In this case, the electric field is highest at the disc which supports the deposition substrate. This provides the energy needed to achieve electrical breakdown of the gases contained within the growth chamber and cause the formation of a plasma adjacent to the deposition substrate surface, as will be detailed further below. The 400 MHz electrical energy may be provided by radio-frequency generator  20  that embodies controllable power output, a coaxial cable for transmitting energy from the generator, an electrical impedance matching device to accomplish efficient coupling of energy from the generator to the powered electrode structure, and equipment for monitoring the amounts of incident and reflected energy in the system, not shown but well known to persons of ordinary skill in the art. 
     A counter electrode,  26  formed from a molybdenum screen in the shape of a disc having a diameter of about one inch, consisting of molybdenum wire having a wire gauge of approximately 16 and a wire/inch weave of approximately 16, is supported parallel to, and spaced approximately 0.5 inch away from, the exposed face of the substrate support disc. This counter electrode  26  is connected to electrical ground (sown as the chamber wall in FIG. 1) and assists in the concentration of electric fields at the deposition substrate  14 , thereby facilitating the breakdown of gas and formation of plasma in the desired region. While the counter electrode  26  is a convenient adjunct to the invention, reducing the criticality of the dimensions of the powered electrode, the present invention is operative without such an electrode. 
     Quartz-halogen radiant heating lamp  16  of a type well-known in the art, commonly used and herein employed to adjust the temperature of the deposition substrate to the desired value prior to plasma ignition is placed behind the molybdenum screen counter electrode  26 . Radiant energy proceeds from the quartz heating lamp through the molybdenum screen counter electrode  26  and impinges on the deposition substrate  14 , causing its temperature to increase. The deposition substrate temperature is monitored, and the quartz heating lamp is controlled so as to achieve and maintain the desired temperature at the deposition substrate  14 . It will be apparent to those skilled in the art that this controlled heating system may be altered or replaced by any of a number of other well-known means for achieving substrate temperature control, including resistive radiant heating, resistive direct heating, induction heating, and control of substrate heating by control of the power applied to achieve plasma formation. 
     A silicon wafer common in the industry having a diameter of about 1 inch and a thickness of about 0.5 mm which has been prepared for diamond deposition by nucleation enhancement means well-known to the art (in this case, minor abrasion with 1 micron diamond abrasive) is employed as substrate  14  and is placed on the powered electrode facing the counter electrode. The deposition chamber  10  is closed, and gases are evacuated from the chamber by means of a vacuum pump included in chamber exhaust and pressure control  28 . When a pressure of 0.01 Torr or less has been achieved, gases suitable for diamond deposition are admitted to the chamber until the pressure is about 5 Torr, at which pressure the atmosphere is maintained by means of a pressure transducer, a pressure controller, and a controlled valve in the chamber gas exhaust line included (but not shown) in chamber exhaust and pressure control  28 , all configured in a manner well understood by persons of ordinary skill in the art. A suitable gas mixture and flow rate has been found to be 200 standard cubic centimeters per minute (sccm) of hydrogen and 10 sccm of methane from gas supply  30 , each gas having a purity level of not less than 99.999%. Other gas compositions known to the art of diamond CVD are operable, and this particular mixture is specified as illustrative and operable without limitation thereto. 
     The quartz heating lamp  16  is energized to bring the deposition substrate  14  (the silicon wafer) to the desired temperature, in this case about 750 degrees Centigrade. This temperature is within the broad range of temperatures known to support diamond CVD and is specified without exclusion of other suitable temperatures known in the diamond deposition art. 400 MHz energy is then applied to the powered electrode to cause the ignition of a plasma between the powered electrode and the counter electrode. It has been commonly observed that plasma ignition occurs when at least 50 watts of energy is applied. When plasma ignition has been achieved, the chamber pressure control system is manipulated to cause a slow (typically 10 torr/minute) increase in pressure to the deposition pressure of 100 Torr. During this pressure increase, the 400 MHz energy source is controlled to increase the amount of applied energy to sustain the plasma between the powered electrode and the counter electrode. As the pressure is increased, 400 MHz energy is delivered in increasing amounts and contributes to substrate heating. Accordingly, the quartz heating lamp 16 is automatically controlled to maintain substrate temperature at approximately 750 degrees Centigrade. While the particular power required to sustain the plasma will vary with the details of each individual apparatus, it has been observed that about 200 watts of 400 MHz energy is adequate to sustain a plasma as described at a pressure of about 100 Torr. 
     As the chamber gas pressure increases from 5 Torr to 100 Torr and additional 400 MHz energy is applied, it is observed that the plasma maintains its diameter of approximately 1 inch but shrinks from the space between the two electrodes to form thin plasma regions or “skins” on each of the powered electrode and the counter electrode. Measurements have shown that at 100 Torr, the plasma on the powered electrode has a thickness of approximately 2 mm, and is so intimately adjacent to the deposition substrate surface that it is difficult to determine the distance between the surface and the plasma, the distance being less than 1 mm. This relationship is completely novel in the art of diamond CVD and underlies the efficacy of this invention. 
     After maintaining deposition at 200 watts of applied energy for 3 hours, all energy inputs to the process are shut off and the apparatus is allowed to cool to room temperature. The chamber  10  is evacuated and filled with air. The chamber  10  is opened and a diamond layer is found to have grown on the deposition substrate  14  to a thickness of approximately 84 microns. This represents a deposition power efficiency of approximately 0.8 KwHr/carat, approximately 7.8 times (780%) as efficient as the known state-of-the-art maximum of 6.26 KwHr/carat. The raw composite growth efficiency is 0.00792. Diamond growth is also noted on the counter electrode  26 , the thickness being less than that noted on the powered electrode. Diamond growth on the counter electrode  26  has been omitted from the efficiency calculation, rendering that calculation conservative. The present invention contemplates reactors designed so as to make use of the diamond material grown on counterelectrode structures to provide enhanced utility. 
     Another actual exemplary process according to the present invention is shown with reference to FIG.  2 . Because the apparatus for performing the process described with reference to FIG. 2 is similar in nature to the apparatus shown in FIG. 1, elements in FIG. 2 which correspond to elements in FIG. 1 will be designated by the same reference numerals used in FIG.  1 . 
     Accordingly, a suitable metallic deposition chamber  10  is provided having a chamber exhaust and pressure control system  28  for control of atmospheric pressure and composition. As in the embodiment discussed previously, the rod  22  and substrate support  12  are provided for supporting and energizing a deposition substrate  14 . The temperature of the deposition substrate  14  may be measured and controlled as in the previous embodiment by temperature measurement and control system  18 . Energy of a frequency of approximately 150 MHz is applied from a generator source to the structure holding the substrate and thereby to the substrate itself. Substrate  14 , comprising a silicon wafer 8 inches in diameter treated for diamond nucleation by means well-known in the art, is placed on the rod  22  and support  12  or other structure suitable for holding such a wafer and fabricated from a material compatible with the requirements of diamond chemical vapor deposition. One such material is molybdenum, with others being tungsten, silicon carbide, silicon nitride; or others known to the art. A counterelectrode  26  having a disc geometry with a diameter of approximately 8.50 inches is disposed in opposition to the substrate  14 , and is separated from the substrate surface by approximately 0.25″. 
     The deposition chamber  10  is evacuated to a base pressure of less than 0.01 Torr and process gases consisting of hydrogen and methane are admitted to the deposition chamber from gas supply  30  at a mixture ratio of 95% hydrogen, 5% methane, and the chamber pressure is regulated at 5 Torr. When 5 Torr pressure is reached, the 150 MHz source is energized and a plasma is observed to cover both the deposition substrate  14  and the counterelectrode  26 , and to fill the space in between these two structures. 
     Chamber pressure is slowly increased to 150 Torr, with concurrent increase in the power level of the 150 MHz source, and with concurrent adjustments of the impedance matching device (not shown) to maintain a good electrical match between the power source  20  and the deposition system. As pressure increases, the plasma is observed to fade from the interelectrode space and to persist as a thin structure on the deposition substrate  14  and on the immediately opposed surface of counterelectrode  26 . At a pressure of 150 Torr, approximately 75 kW of 150 MHz energy is required to maintain a uniform plasma over the deposition substrate  14 . 
     After a duration of seven hours, the deposition system is shut off, and allowed to cool. A diamond film is observed to have grown over the silicon deposition substrate to a thickness of approximately 120 microns. The power deposition efficiency is calculated to be 1.4 kWHr/carat of diamond deposited. The raw composite growth efficiency is 0.00832. The normalized composite growth efficiency is calculated to be approximately 17.6 times, or 1780%, of the efficiency of the 100% reference growth efficiency of the arc jet method. 
     Presentation of the foregoing illustrative embodiments is not by way of restriction to those methods. For example, numerous extensions are contemplated of those embodiments in which energy is provided through application of one or a combination of two or more other sources such as lasers or other illumination sources, electromagnetic radiation outside the visible spectrum, radiation from nuclear sources, pressure or shock waves, thermal energy, energy from chemical reactions, etc. Processes in which reactants are supplied to the atmosphere to which energy is supplied by through phase change(s) from liquid to vapor, or from solid to vapor, or by finely subdividing reactants in the solid or liquid form in order to disperse them in the growth atmosphere are also contemplated according to the present invention. 
     Following synthesis of raw diamond material, manufacturing finished diamond materials may be achieved through use of techniques such as laser cutting to achieve the requisite shape and dimensions, mechanical grinding and polishing to produce the required thickness, flatness, parallelism, and surface finish, and sputtering and/or physical vapor deposition to deposit those metal coatings that may be needed to support solder or braze attachment between the diamond and other components. These techniques are all well known to those skilled in the art, and are available from a wide range of commercial suppliers of equipment for fabricating ceramic materials. 
     While embodiments and applications of this invention have been shown and described, it would be apparent to those skilled in the art that many more modifications than mentioned above are possible without departing from the inventive concepts herein. The invention, therefore, is not to be restricted except in the spirit of the appended claims.