NL8201632A - CHEMICAL METHOD. - Google Patents

Abstract

A deposition process comprises intermingling a reagent gas in a metastable state with a sample gas, causing the latter to be energised to neutral atoms. or molecules in an excited state, providing a light source to supply further energy in an atm. corresponding tothe difference between that of the excited and ionised states of the sample gas, thus causing selective ionisation of the latter, and imposing an electrical or magnetic force on the ions to cause them to deposit from the gas stream on a substrate as stable atoms. Metals, non-metals and molecules may be deposited in any alternating order to give a sandwich of 100% pure individual layers. More than one metal can be deposited simultaneously to form an alloy layer. Monomers can be deposited as ions so that polymerisation occurs. Catalyst layers, microelastomeric components, optical surfaces and doped single crystals may be formed. The coatings are ultra-pure and of controlled thickness and the process is generally operable at room temp.

Description

A i

S

Chemical method.

The invention relates to a new way of carrying out chemical reactions by incorporating selected energy forms into the reaction zone by new means. Using this principle, many new processes are created, which can be applied in a large number of different industries. The new process can generally be carried out at room temperature, which has advantages in the manufacture of certain sensitive products, including uniformly doped semiconductors, new catalysts, pure gases, high purity substances of all kinds, carefully applied coatings, new polymers, combustion improvement , difficult separation, petroleum refining and carrying out any reaction, involving the introduction of certain types of energy.

A special case is a method for manufacturing coatings of selected metals, non-metals and other molecules. Multilayer coatings can be formed from virtually any combination of fabrics. The purity of the material of each layer can be as high as 100% and the thickness of each layer can be controlled to a single atomic or molecular layer.

It has heretofore been impossible to produce bodies or deposits of metals, non-metals, crystals and substances in general and to obtain a purity of about 100%, especially when the processes involved are carried out at ambient temperatures. It has also been found that it is impossible to dope these bodies at ambient temperatures since doping requires diffusion and requires high temperatures to diffuse the dopant into the body. For example, ultra-pure silicon must be heated to dop it by diffusion methods. However, heating for this purpose causes imperfections in the crystalline silicon, resulting in large numbers of unusable products 8201632 «* -% 4 - 2 -« ►.

According to the invention a metastable gas reagent is formed, mixed this gas reagent with a gas sample, whereby the latter comes into an excited state by energy absorption from neutral atoms or molecules, this energy-containing gas sample is selectively ionized by introducing extra energy in an amount , which corresponds to the difference between that of the excited and that of the ionized state of the gas sample and exerts an electric or magnetic force 10 on the ions to remove them from the gas stream as stable atoms in an accumulation zone, e.g. a substrate in a container separate from the main gas stream. The additional energy can be added in various ways, for example, with a laser-type light source, or with hollow electrodes, magnetic or electrical charges, or the like.

The invention has numerous applications for products or methods in many industries, many of which will be discussed in this description.

Going further into the details of the invention, it can be said that it comprises the following principles: 1. It is possible to generate large numbers (approx. 10-14 / 10 sec) of so-called metastable atoms and / or molecules by neutral or ionized atoms or molecules in the ground state in the gas phase by conducting a voltage of 200 to 300 V. Optimum metastable production usually occurs when the gas reagent (i.e. the atoms or molecules from which the metastable atoms or molecules are formed) is at low pressure, such as 1 to 5 torr. An atom, molecule, or ion is said to be metastable when it has additional energy above its ground energy state and when it tends to slowly lose its energy excess from radiation processes. The energy excess, which has a metastable, is usually transferred in whole or in part during inelastic collisions.

35 2. Due to the relatively long life of 8201632 \ - 3 - ί * κ metastables, they can be easily contacted with metal, nonmetal, or gas phase molecules so that through inelastic collisions, the energy excess of the metastable gas reagent is imparted to them. transferred. Thus, energized metals, non-metals and / or molecules can become a neutral atom or molecule in the excited state or an ionized species.

3. Neutral atoms or molecules in excited states (ie with excess energy) can be further excited up to the point at which an electron is ejected (thus forming the atomic ion or molecular ion) by adding more energy in an amount , which corresponds to the energy difference between the ionized state and the excited state of the species concerned. Often this energy difference is small and can be provided by a light source (eg, a color laser, etc.), which emits in the ultraviolet and visible portion of the electromagnetic spectrum. That is, by irradiating a collection of neutral atoms or molecules in the same excited state (ie the same energy excess) with mono-chromatic radiation, the energy of which exactly corresponds to the energy difference between the excited and ionized state, only those atoms become or molecules ionized.

Due to the unique energy difference between an excited state of a particular atom or molecule and its ionized state, almost absolute selectivity is achieved. Often the above energy difference can be changed using a different gas reagent, because each gas reagent is composed of metastable atoms or molecules, whose energy differs from one gas reagent to another. For example, the characteristic metastable energy for some 3 selected gas reagents is as follows: helium (2 S) 19.7 eV, 3 3 + argon (3 Pq 11.7 eV and nitrogen (Σ ^) 6.1 eV. An additional measure selectivity can be achieved by using a gas reagent, the metastable energy of which differs in an amount from the ionization energy of the metal, not metal or molecule, of the metal involved, such that any other material, except the data subject is not possible.

4. The ions produced in this way are charged particles (by definition) and can therefore be made to move in a certain desired direction by the application of an electric or magnetic field and to be collected as a thin uniform film at a certain desired direction. location. Furthermore, by correct selection of the shape of the applied field, mass discrimination can be obtained, although it is rarely necessary with this method.

In summary, the invention can be described as follows: an argon flow (2000 µm mill / pass) is established in a mild vacuum (1-5 torr). The argon (ΡΛ «) metastable o * i3 15 state 11.7 eV is generated in large amounts of 10 -10 / sec when the argon is passed through two annular electrodes over which 200-300 Vdc is applied. These metastable argon atoms, further referred to as a gas reagent, are contacted with a molecule of interest designated as a gas sample (ie, W (C0) g, Ni (C0) g, silanes, per-fluorobutane, etc.) to which it metastable argon gas releases its energy excess to the gas sample. Many complex reactions take place in such an energy-rich environment, but the formation of the metal, non-metal or molecule in a neutral, high-energy state and still in the gas phase is predominant. The output power of a nitrogen laser-pumped, pulsed tunable color laser is adjusted to the wavelength corresponding to the exact energy required to cause ionization of the gas sample given energy from its neutral high energy state. The configuration of the cavity or container in which the above takes place is such that an electric or magnetic field can be applied to connect the site of formation of the ions of interest to the site where they must be deposited, without including other nonionic products present in the reaction zone. The layers thus deposited on a suitable target can be controlled in thickness to an atomic or molecular layer by controlling the rate at which sample ions are formed. Layers of known uniform thickness of metals, non-metals and molecules can be deposited in any order, thus obtaining sandwich-type layers.

Optionally, two or more metals can be deposited at the same time, thus forming an alloy, Eighty layer, or other molecules, such as monomers, such as ions can be deposited on a surface, such that polymerization occurs and certain chemical reactions can be observed. which are known to proceed via an ion, at a particular location and at a certain controlled rate.

The following examples illustrate the invention.

Five examples of the present method are given. The first refers to the non-metal silicon and the second to the metal tungsten.

20

Example I

By passing a 2000 micromole / minute stream of helium gas past electrodes over which 200 VDC has been applied, 10 to 1014 metastable helium atoms (in the 2 ^ S state) are formed. If a volatile silicon compound, such as silan, is mixed in the flow of metastable helium atoms by a collision process, the metastable energy is transferred to the silan to form neutral silicon atoms in the excited state. The energy difference between the excited neutral atom and the ionic form of the atom is 3.18 eV, which is equivalent to the energy of light with a wavelength of 390.53 nm. Thus, if light with a wavelength of 390.53 mn is incident on the neutral excited silicon atoms, they absorb the incident light and are thereby ionized. By applying an electric or magnetic field graph between the ions and a suitable target, the ions and only the ions migrate to the target, where they take up an electron and are deposited evenly as neutral atoms in the ground state.

5

Example II

Tungsten is taken as an example of a metal. The same method is used for the metal tungsten (as described above for silicon). The volatile tungsten compound used is tungsten hexacarbonyl W (CO) g. Neutral excited tungsten atoms are formed in the same way as with silicon. The energy difference between the neutral, excited tungsten atom and its ionic form is 2.54 eV, which is equivalent to the energy of light with a wavelength of 489.73 nm. Thus, when light of 489.73 nm wavelength is incident on neutral excited tungsten atoms, they absorb the incident light and are ionized. As above, an electric or magnetic field gradient causes migration of the ions to the target, where they take up an electron and are evenly deposited on the target surface as neutral tungsten atoms in the ground state. Table A summarizes the energy relationship described above.

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Example III

P-N jump - photocell.

The following example is a principle application of the invention.

5 Photocells have been extensively researched in recent years as means of generating electrical energy because of the need to generate electrical energy in remote places, such as space. In the past, using photocells for energy production was very expensive (10 to $ 175,000 / kilowatt). Said high costs resulted from the necessity to use very complicated and expensive manufacturing methods, if at least the organ could be manufactured. Even in this case, the number of failed products was as much as 90%. With interest in photocells also beginning to extend across the commercial area as a means of providing an alternative energy source for fossil fuels, any cost reduction in photocell production is welcome.

The example discussed below relates to a silicon matrix-based photocell in which the P layer is silicon doped with antimony and arsenic or phosphorus. The P and N layers are formed to result in a sand-wich configuration.

The application of the principle of the invention provides PN jumpers (photocells, etc.) in a manner which: 1. is performed at ambient (room) temperature and thus makes the use of the high-temperature induction furnaces superfluous. required by current processes, 2. the doping process is carried out continuously and in a precisely controlled manner at room temperature, resulting in dopant concentrations at the bottom of the silicon layer equal to those at any other depth. found in the layer and thus obviates the normal non-8201632 yr »- 9 - linear diffusion of the dopant as a function of depth, which is always due to the current high temperature diffusion process, 3. allows the formation of a PN hopper 5 with separately controlled layer thickness, dopant type and dopant concentration, so that the substrate (the surface on which the photocell is attached), when h Once assembled, not handled, or otherwise physically removed from the device used to deposit the P-N jump material 10.

In this example, for illustrative purposes, the N-dopant is boron and the P-dopants are antimony and phosphorus. The choice of these dopants does not mean that other dopants cannot be used exactly the same way, ie by applying the principle of the invention. This example differs from the foregoing as follows: in the previous example, the manner in which a metal or non-metal could be purified to a very high degree was given, but the example below discusses the ways in which a controlled amount of a particular can incorporate contamination and no others into a high purity matrix, the amount of contamination determined being very small (up to the order of parts per 100 trillion).

The silicon source is selected from a wide variety of volatile silicon compounds, such as tetramethyl silicon. The volatile compounds are selected because they have very high vapor pressures or readily form gases at room temperature.

An amount of silicon compound, which is 30qui-valent with 1 or 2 grams of silicon, is placed in a closed vessel, which has 1. temperature control, which can be adjusted within ± 0.01 ° C from 100 ° C to -200 ° C and 2. can be connected to a manifold via a metering valve.

8201632 - 10 -

The valve is initially closed so that gas solids in the vessel can be brought into thermal equilibrium with the vessel. The temperature control is adjusted to the temperature, which results in the desired pressure for the gaseous silicon compound, tetramethylsilicon (IMS), for example, 27 ° C resulting in a TMS gas pressure of about 150 mm Hg.

The silicon source is taken from a large number of boron compounds, such as the hydrides and diborane, which are volatile. The volatile compounds are selected because they have high vapor pressures or readily form gases at room temperature. An amount of diborane equivalent to 1 or 2 mg of boron is placed in a closed vessel with the same properties as the vessel containing the silicon compound and the boron-containing vessel is connected to the same manifold so that the two gases can be added as required be mixed. Since the amount of dopant is usually very small, parts per trillion or less, relative to the silicon, the low temperature capabilities of the boron-containing gas must be used. That is, keeping the temperature at about 165 ° C results in a vapor pressure of about 1 to 2 mm Hg. Therefore, if the gases, TMS and diborane were allowed to mix freely in the manifold at their respective vapor pressures, there would be about 1 part borane per 25 trillion with respect to TMS. In order to further reduce the diborane concentration, the metering valves must be used, which separate each vessel from the manifold and apply a mild vacuum to the manifold. Any low borane concentrations in the flowing mixture of the two gases can be achieved in this way. The mild vacuum applied to the manifold provides the driving force or means for transferring the gas mixtures to other locations in the device.

As above (ie in the previous example), a gas is selected as helium to form a gas reagent. It is recalled that by passing approximately 2 moles / mimxut helium through a conduit, such as a gas tube, around which two annular electrodes are spaced 3 to 5 cm apart at some convenient point and over which 200 Vdc is applied, energetic or excited neutral helium atoms are formed. These neutral excited atoms are hereinafter referred to as the metastable gas or gas reagent.

The manifold into which IMS and borane is flowed is connected to the glass tube or conduit where the metastable gas is formed so that the IMS and borane mixture flows into the metastable gas, where energy of the metastable atoms (neutral excited atoms) is transferred to IMS and diborane. This configuration is selected (rather than the one where the mixture of both TMS and diborane and helium mix together to form the reagent or metastable gas) so that no silicon and boron ions are formed for irradiation with light the wavelength or wavelengths corresponding to or corresponding to energies or energies equal to those necessary for ionizing silicon and boron from their neutral excited states. The reason for this is that very high purities and high coating speeds can be achieved by avoiding indistinguishable ionization. It should be noted, however, that under certain circumstances it may be convenient to form ions from either the dopant or silicon by mixing with the helium to form the metastable gas, namely when there is a need or desire no light source such as a laser and / or low purity standards can be tolerated, but high-30 coating rates are required. However, in this example, such a case will not be considered in detail. In either case, however, when energy is transferred from the metastable gas to TMS and diborane, the excited neutral silicon and boron atoms are formed. Table B 35 summarizes the energy content of the most prominent neutral states and ionized states of silicon, boron, phosphorus, antimony and arsenic. Included in the table are the different energy differences between the excited neutral and ionized states of.

5 the elements mentioned.

TABLE B

Element and Energy-Energy difference between 10 state neutral and ionized state A ° eV eV A °

Matrix

Silicon: 15 Neutral 2881,578 4,303 Ionized 1533,550 8,121 3,818 3247,774 P Layer Doping Agent _

Boron: 20 neutral 2497.733 4.965 ionized 1362.460 8.296 3.33, 3722.606 N-layer dopants _ .......

Antimony: 25 neutral 2060,380 5,995 ionized 1435,351 8,639 3> 644 3402,854

Phosphorus: neutral 2534,010 4,893 30 ionized 1182,755 10,484 5> 59, 2218> 021

Arsenic: neutral 1890,500 6,559 ionized 1264,010 9,810 3 3 314 211 35 8201 632 V * - 13 -

At this point, the gas containing neutral, excited silicon and boron can be passed through an electric and / or magnetic field to remove unwanted ions, which may be formed during energy transfer from the metastable gas, such as impurities, whose ionization energy is smaller than that of silicon and boron. This method results in a very high purity of the gas flow. Actually, to obtain the highest purity, a gas such as helium has been selected due to its high energy content in the metastable state of about 21 eV, thus causing efficient ionization of impurities (with low ionization energy and ineffective ionization of atoms or molecules with high ionization energies).

The gas, which contains the silicon and boron atoms in their excited neutral states, is then irradiated with intense light from a source, such as a hollow cathode lamp or a laser (tunable color type, for example). The light must be monochromatic (or nearly monochromatic) with a wavelength of 3247.774 A ° or 3.818 eV. Depending on the intrinsic intensity of the light source and the concentration of neutral, excited silicon and boron atoms, either a single passage or a multiple passage of the light path through the gas can be used. A multiple pass optical configuration is preferred.

When neutral excited silicon and boron absorb light of this wavelength, the respective ions are formed because light with a wavelength of 3247.774 A ° meets the ionization energy needs of silicon in its longest living neutral state and exceeds that of boron 30 in its longest living neutral state.

The ions thus formed, while still in the moving gas stream, are passed through an electric and / or magnetic field and the ions are deflected from the stream (through their interaction with the field) and thereby to a surface suitable for coating focused.

8201632 - 14 -

If further purification of the gas stream is required for the point at which silicon and boron ions are formed (namely, upon irradiation with monochromatic light having a wavelength of 3247.774 A °), the gas stream may first be irradiated with monochromatic light having a wavelength of somewhat less than 3722.61 A °. By doing this, any unwanted atomic or molecular species that can be ionized by light of 3722.61 A ° can be removed from the gas stream by passing it through an electric and / or magnetic field located between the light sources of 3722.61 A ° and 3247.774 A °.

The ions of silicon and boron are deposited on a negatively charged target, where they form a crystal or crystals, while taking up an electron and thus becoming neutral, in a crystal lattice. The deposition process can be carried out for as long as is necessary to obtain the desired thickness.

Once the desired thickness of P-layer has been deposited, the N-layer is deposited on top of the P-layer without having to remove the substrate P-layer for inspection or polishing. Any N-layer dopant or combination of such agents can be used to form the N-layer with silicon as the matrix. The method and device used are exactly the same as described for the formation of the P-layer using boron, except that the wavelength of light 25 for the formation of the ions is chosen such that it corresponds to the energy difference between the neutral excited and ionized state of the particular atoms used.

A further refinement, which can be used to obtain a maximum purity of the atomic species concerned, is worth mentioning. Although a particular atom, silicon, is used for explanation, one can of course apply this refinement to any other atom, for example germanium, and so on.

Once the silicon atom is formed in its excited neutral state, other neutral excited atoms of an undesired kind can also be formed. If these contaminating atoms can be ionized by 3247,774 A ° light, they can be ionized together with the silicon. Then irradiating all neutral excited atoms with another monochromatic light source, the wavelength of which corresponds to an energy slightly less than that required for the ionization of the neutral excited silicon atoms (3250 A °). silicon atoms remain unchanged with the gas stream, but the other neutral excited atoms, which can be ionized, will then be and can be deflected from the gas stream by applying an electric and / or magnetic field. It is also clear that all kinds of other neutral excited atoms, as well as silicon, go with the gas stream, that when the monochromatic light of 3247,774 A ° irradiates the current, only the neutral excited silicon ions are ionized and all other atoms with the gas stream come along. Thus, the refinement discussed provides an energy filter of approximately 3 A °, so that those neutral excited ions, which can be ionized at lower energies than neutral excited silicon, are ionized, and those neutral excited atoms, which need more energy for ionization then neutral, excited silicon, never become ionized and go with the gas stream to the drain or collection.

Four further examples will now be given of the application of metastable gases to important processes, namely: 1. metal purification with two lasers.

2. combustion.

30 3. catalyst formation.

4. hydrocarbon cracking.

Example IV.

Metal purification with two lasers.

A summary of this application can thus be formulated 8201632, 4. y - 16 - a gas, such as helium, is passed through an electric field to form a large concentration of the excited, neutral form of helium, hereinafter designated 5 as metastable helium atoms. A volatile form of a selected metal, nonmetal or other molecule, hereinafter referred to as a gas reagent, is introduced into the flow of metastable helium atoms, causing energy transfer from the metastable atoms to the atoms / molecules of the gas reagent, whereupon Thus increasing the energy of the reacting molecules / atoms to an energy state, hereinafter referred to as a neutral, excited state (whose energy is less than that required to cause ionization of the atoms / molecules of the gas reagent By irradiating the neutral, excited atoms / molecules of the gas reagent, the light of a wavelength exactly corresponding to the energy difference between the excited neutral reagent species and the ionized reagent species, ionization occurs in those species in the reagent gas for which the sum of the metastable energy and the energy of the irradiating light is equal to or goes out above the ionization energy. Thus, any pollutant species in the gas reagent whose ionization energy requirement exceeds this sum is not ionized and therefore eliminated as a candidate for thin film deposition, since deposition in the present invention depends on ions. It is also clear that pollutant species in the gas reagent, the ionization energy of which is less than this sum, are ionized together with the reagent and are consequently deposited in the thin film and thus considered impurity. When reorganizing the method of applying the invention to film deposition and expanding the idea on which the invention is based, it is possible to prevent the incorporation into the thin film of pollutant species whose ionization energy requirement is less than or equal to that of the reacting species. The discussion below explains the method for a mixture of nickel, iron 8201632-17 and tungsten, the intention being to produce a thin nickel film, but one without inclusion of iron or tungsten. In view of Table C and taking into account the details of the invention, it is clear that once the metastable nickel gas reactant is formed together with polluting iron and tungsten, irradiation with light of 6316.9 A ° causes ionization of the neutral excited nickel and iron species, but does not cause ionization of the neutral, excited wolf window species.

10

TABLE C

Element Neutral Ionized Energy excited (A °) state (A °) difference (A °)

_eV_eV_eV

15 W 4008.8 A ° 2204.5 A ° 4897.3 A °

3,093 eV 5,625 eV 2,532 eV

Fe 3581.2 A ° 2382.0 A ° 7114.2 A °

3,463 eV 5,206 eV 1,743 eV

20

Ni 3414.8 A ° 2216.5 A ° 6316.9 A °

3,631 eV 5,594 eV 1,963 eV

Thus, after deposition, it appears that the thin nickel-25 film contains only one of the two contaminating species, ie iron, but no nickel. However, if the neutral, excited reagent species and the contaminating species are first irradiated with light with a wavelength greater than 6316.9 A °, the contaminating species iron is ionized, but the remainder is not. The iron ions can then be electrically or magnetically deflected from the gas reagent species (nickel) and the only remaining contaminating species (that is, the tungsten). The remaining mixture is then irradiated with light of a wavelength less than or equal to 6316.9 A% but more than 35 4897.3 A °, thus forming nickel ions, but no tungsten ions. 8201632-18. In this way, a reagent species whose ionization energy requirement is between those of two contaminating species can be separated and deposited as a thin film free of inclusions or contaminants.

5 In reality, the process could be performed as follows:

By passing a 2 mmole / minute stream of helium, contained in a glass conduit, through 2 annular electrodes over which 300 Vdc is applied, approximately 10 10 metastable helium atoms are formed per second. The gas reagent (composed of gaseous reagent Ni (CO), (nickel carbonyl) and two

O

impurities Fe (C0) g and W (C0) g, (iron carbonyl and tungsten carbonyl, respectively) are introduced into the flow of metastable helium and mixed by turbulence and diffusion. The neutral excited states of each metal are formed by impact energy transfer and / or Foster processes and helium is left in its neutral ground state. The flow of reagent gas, which now contains the neutral excited species of iron, nickel and tungsten, is conducted by differential pressure across the glass conduit to a point where the flow is irradiated with light of wavelength greater than 6316.9 A °. (e.g. 6500 A °), on which the neutral, excited iron species is ionized, but the neutral excited nickel and tungsten species are not. The ionized iron is attracted to a negatively charged target within the glass tube and thereby removed from the gas reagent. The flow of gas reagent, which now contains only the neutral excited species of nickel and tungsten, is passed through the glass line by differential pressure to a point where the flow is irradiated with light of a wavelength less than or equal to 6316 .9 A °, but not less than or equal to 4897.3 A °, on which the neutral excited nickel species is ionized, but the neutral excited tungsten species is not. The ionized nickel is drawn to another negatively charged target within the glass lead, where it is deposited and forms a nickel layer, which is free of iron 8201632-19 and tungsten, because the iron was first turned off as described above and the tungsten was never ionized and as such is not deposited with the nickel.

5 Example V

Improved combustion of hydrocarbons

An example will now be given of a new way in which the metastable gases nitrogen and oxygen can be used for a more efficient combustion of hydrocarbons. Combustion efficiency is related to the amount of useful energy that can be extracted from the combustion products. When not using the present invention, a combustion engine consumes 15 parts air per part fuel, but when using the present invention, the combustion engine consumes 33 parts air per part fuel. Thus, the combustion efficiency is increased by a factor of 2.2.

The new method of combustion of hydrocarbons provides: 20 1. the production of more useful energy per unit mass of fuel than the usual combustion methods, 2. more complete combustion of fuel and therefore smaller amounts of polluting or harmful gases 25 (ie NO, NO2 , CO, and so on) in the exhaust, 3. the need for the necessary expensive provisions to combat air pollution in cars, 4. cheaper fuel consumption.

30

The new combustion method involves conducting the fuel oxidizing agent (i.e., in in air) through an electrostatic or magnetic field created by the application of a DC voltage across two annular electrodes extending axially in each other, which channel surrounds 8201632 - 20 - through which the gas mixture passes on its way to the combustion chamber. The resulting gas mixture has a high concentration of "metastable" oxygen and nitrogen molecules. Since the physical nature of metastable atoms and / or molecules has been set out above 5, no further discussion of their physical nature will be given, but it is worth noting that the metastable atoms and / or molecules are not ions, so that the process does not depends on ionization or a plasma.

When metastable energy is transferred through collisions from oxygen or nitrogen or both to gas phase fuel and / or fuel aerosol (as a droplet), the energy increase results in a reduction of "activation energy" for combustion at vapor phase fuel molecules and an increase in the vapor pressure of the fuel in the fuel aerosol particles. The latter observation stems from the fact that liquid phase fuel does not burn, but instead burns vapor phase fuel. Thus, when the fuel has not evaporated well (ie, in an aerosol), a significant amount of heat from combustion of the gas-phase fuel is required to provide the evaporative heat for the fuel droplets in the aerosol. The heat used to evaporate fuel droplets cannot be converted into energy. When a fuel droplet in the aerosol contains additional energy, such as collision-transmitted metastable energy, an increase in the vapor pressure of the fuel aerosol droplet occurs due to the generally accepted and widely applied principle of thermodynamic equilibrium. An open chemical system constantly seeks the state of thermodynamic equilibrium because this is by definition the most stable state. Thermodynamic equilibrium is achieved by redistributing excess energy over the electronic, translation, vibration and rotational energy of the open chemical system. Thus, if metastable energy is added to an aerosol fire-35 dust droplet, it enters the electronic energy of the system from 8201632 - 21, but, since the system tends to thermodynamic equilibrium, the excess electronic energy becomes rapid (approx. 10 ^ sek.) redistributes over the translation, vibration, and rotation energy. These are the forms of energy which, in decreasing order of importance, have the most influence on the vapor pressure of the fuel droplet.

Both by reducing the activation energy to burn gas-phase fuel molecules and by increasing the vapor pressure of the aerosol fuel droplets, the factor 2.2 increases the combustion efficiency.

The practical implementation of this system is described by means of a four-stroke internal combustion engine as in an automobile. The fuel air mixture 15 used therein is supplied to each cylinder through the inlet manifold.

Opposite each inlet opening, to which the inlet distributor is mechanically connected, an ordinary airtight electrical supply is provided on this distributor. The electrical supply is isolated from the distributor. A metal bar of 1 mm diameter 20 is welded to the electrical connection on the inside of the distributor. The length of the bar is adjusted so that it does not interfere with valve operation. The metal of the bar is selected to have a strong electronic energy function and is inert. In this example, tantalum 25 was used. A positive connection to a 300 V DC voltage is attached to the outdoor section of the electrical connection. The negative connection of the voltage supply is connected to the metal of the distributor. This completes the electrical circuit, which includes the air between the tantalum rod and the interior metal surface of the manifold, through which the fuel-air mixture flows during operation. The voltage supply was set to an applied voltage of 12 V DC and an output voltage of 300 V DC at a power of 10 watts.

As a result of this operation, 8201632 - 22 - one achieved greater energy and less harmful exhaust gases, the exhaust gas mainly consisting of carbon dioxide and water vapor.

Example VI

Catalyst manufacture.

Many industrial processes rely on catalysts, such as the metals platinum, rhodium, silver, nickel, gold, iron, copper, zinc, and so on. Even alloys of some of these metals are used as catalysts. It is true that all kinds of the above-mentioned catalysts can be manufactured according to the described method, but the method will only be explained to a platinum catalyst in combination with the oxidation of ammonia to prepare nitric acid.

A platinum mesh is used as a catalyst in the industrial process of oxidizing ammonia. The majority of the platinum mesh mass serves to provide a mechanically stable physical structure and a large internal surface. Due to the cost of the metal, it would be desirable to apply a platinum coating to a much cheaper mechanical support.

Usually, a catalyst is not consumed in the course of a reaction which it drives. However, with platinum mesh used in the oxidation of ammonia, the platinum appears to be consumed. The reason why this occurs is that impurities in the platinum mesh react with ammonia or nitric oxide or nitric acid, but the platinum does not. The result is a physical erosion of the platinum mesh, causing it to decompose and replacement with a fresh mesh. Therefore, if one could provide ultra-pure platinum on a mechanically stable substrate with a large internal surface, such as aluminum oxide (Al, the catalyst could continue indefinitely and be much cheaper.

This objective is now achieved with the method described below.

8201632 • é · * - 23 -

The method used is exactly the same as described above under Example IV. However, the volatile form of platinum can be platinum hexafluoride (PtFg) or PtCPF ^) ^

The first light source must have a wavelength of more than 5. 2858.8 A °, which removes all impurities, the ionization energy requirement of which is less than that of platinum. The second light source must have a wavelength less than or equal to 2858.8 A °, although not more than 100 A ° less, which causes the ionization of the neutral excited platinum species 10 and no others. The second target can be A ^ O ^ or Quartzwol, which is given a negative static charge. Thus, the platinum ions are neutralized and simultaneously deposited on the substrate to form a surface of the desired thickness of substantially 100% purity. The amount of platinum required is 0.001% of the mass required for the conventional platinum mesh catalyst with a 10 to 100 times longer life.

Example VII

This example describes a new application in the production of petroleum products such as gasoline, jet fuel, fuel oil and the like from crude oil in a manner that does not require a catalyst. Currently, significant amounts of expensive cracking catalyst are required to produce crude oil petroleum products in most of the oil refining processes.

The usual service life of cracking catalysts varies from a few hours to weeks, depending on the quality and chemical properties of the crude to be refined. In addition, the cost of a fresh catalyst charge for a medium-sized oil refinery may, according to Jim Hatten of Texas Eastern Co. amount to $ 400,000. Thus, it is evident that a new crude oil cracking method, which does not require an expensive catalyst, reduces production costs and thereby costs for the consumer.

8201632 - 24 -

The process can be briefly described as follows:

So-called "hydrocarbon cracking" is a non-technical designation for breaking a carbon-carbon bond in the hydrocarbon. The tendency of any chemical bond, such as a carbon-carbon bond to maintain, can be expressed in the bond energy. Thus, in order to break such a bond, at least an acceptable form of energy must be applied to the bond to be broken in an amount sufficient to cause the desired break. Catalysts have been successful in solving this problem. Thus, catalysts have the means of reducing the tendency of the carbon-carbon bond to hold to the point of breakage. Thus, catalytic "cracking" of crude oil to petroleum products can be envisioned as a process in which long chain hydrocarbons (crude oil) are broken into short chain hydrocarbons (petroleum products) using a catalyst which breaks carbon-carbon fractions. bonds in long chain hydrocarbons. The resulting mixture is then distilled in the normal manner.

However, the new invention does not require the use of a catalyst, but a novel way of supplying the energy required to break carbon-carbon bonds is central to the process. The energy source used is a metastable form of one or more solid or inert gases, such as nitrogen, argon, helium, neon, krypton. Due to the abundant presence of nitrogen, this is preferably used, although the other gases work equally well.

A metastable gas molecule or atom contains excess energy in an amount sufficient to produce an excited state which is "metastable", ie, has a relatively long life (0010 milliseconds). If a large collection of metastable gas molecules is present, it is referred to as a metastable gas.

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When such a gas is contacted, that is to say mixed with, hydrocarbons collide between the hydrocarbon molecules and metastable molecules / atoms, the above metastable species having all sufficient energy to break the carbon-carbon bond in the hydrocarbon molecule. The fate of the metastable gas molecule after energy transfer is that it returns to the ground state (i.e. the state of minimum electronic, vibration and rotational energy). Metastable gases are generated by passing a stream of gas molecules / atoms into the ground state through a DC potential gradient or by exposing the gas stream to the microwave field.

In particular, in order to homolytically break a chemical or co-15-valent carbon-carbon bond, 84.4

Kcal per mole are applied to the hydrocarbon. This energy amount corresponds to 3.66 eV. The metastable energy of certain solid and inert gases is shown in Table D below.

20

TABLE D

Atomic / Spectroscopic Metastable molecule notation energy in eV_

He 21S 20.6 25 21 2S 19.82

Ne 3p0 16.7 3p1 16.6

Ar 3p0 11.7 3P2 11 »3 4 5 30 Kr 3p0 10.5 8201632 P2 9’9 2

Xe 3pQ 9.44 3 3P1 8.43 4 3p2 8.31 5 35 N2 (g) 3 * 6.03 - 26 - •

Thus, when nitrogen gas is passed through an annular pair of electrodes over which 200 V DC is applied or through a microwave generator or magnetic field, significant amounts of metastable nitrogen species are produced. The amount of metastable gas produced per unit of time depends on the power of the applied electric field or magnetic field or microwave field, as well as the flow rate of the gas in the ground state by the electromagnetic force (EMF) field. For example, a 1Q 200 V DC 5 Watt EMF field is sufficient to produce 6 x 10 metastable atoms / molecules per 10 minutes. Since the production of metastable atoms / molecules is physically equivalent to an optical absorption process, which depends on instantaneous concentration of gas in the ground state in the field, scaling is easily feasible. Thus, petroleum products are formed at the same rate as that of the production of metastable gas molecules reduced by wall losses and by recombining processes. The estimated loss is less than 10%.

In the case of vapor phase crude oil, such as a fluidized cracking bed in combination with a metastable gas of the above-described type, it is obvious to maintain a 50-50 ratio of metastable gas to crude oil vapor by means of concentric annular nozzles. .

Experimental principle data was obtained with a long chain hydrocarbon, n-decane. When n-decane vapor was mixed with metastable nitrogen molecules by means of a concentric annular nozzle, the following products were obtained: 30 8201632 ♦ · - 27 -

TABLE E

Carbon # a_Relative% _ 1-6 41 7 4.3 5 8 13.4 9 10.7 10 6.7 11 13.0 12 5.7 10 a) include isomers.

Thus, it appears that hydrocarbon cracking can be promoted as described above.

Other preferred applications of the invention are: 1. Catalytic metals deposited on inexpensive substrates.

2. Microelectronic units or components (diodes, transistors, etc.).

20 3. Metal or polymer coatings designed to delay or prevent corrosion and / or wear.

4. Special optical surfaces and crystals.

5. Cheap conductors.

6. Very pure substances of all kinds.

25 7. Replacement of all kinds of epitaxal processes at high temperature.

8. Relatively pure separation of a variety of difficult-to-separate elements including, but not limited to, the rare earths, platinum group metals, rare gases such as argon, neon, etc., hydrogen, helium or other gases, atmospheric gases in general and the halogens.

9. Execution of any chemical reaction, where injection of specific energy types is helpful.

35 8201632

Claims (22)

Process for the production of ultra-pure coatings of metal, non-metal, organic substances, inorganic substances and other substances, characterized in that a stream of gas reagent of helium or argon is passed through two annular electrodes, over which a voltage from 200 to 300 V and this gas reagent comes into contact with a gas sample consisting of W (C0) g, Ni (CO), silane and / or perfluorobutane, whereby the metastable O 10 gas transfers its energy excess to the gas sample under formation of the metal, not metal or other molecule in neutral high energy state, sets a pumped pulsed tunable color laser to the wavelength, corresponding to the precise energy, which to cause ionization of the gas sample, given the energy of its neutral high energy state is required, this procedure taking place in a hollow container, so that an electric or magnetic field is applied in order to achieve an equal adhere some film of the particular ions involved to the site where they are deposited, thereby depositing at least one layer of the selected substance in a controlled thickness on a selected target substrate, the amount of which is controlled by control of the rate at which the ions of the gas sample are formed. 2. A method according to claim 1, characterized in that selected metals, non-metals and molecules are deposited in some alternating order, producing a sandwich of substantially 100% pure individual layers. A method according to claim 1, characterized in that 8201632-29 - that more than one metal is deposited simultaneously to form an alloy layer. 4. Process according to claim 1, characterized in that monomers are deposited as ions on a surface such that polymerization occurs. Process according to claim 1, characterized in that a catalyst layer is deposited. 10 .6. Process according to claim 1, characterized in that coatings are deposited to form microelastomeric components. Method according to claim 1, 15, characterized in that deposits are formed producing optical surfaces. 8. Method of depositing substances, characterized in that a gas reagent in metastable condition is mixed with a gas sample, whereby the latter is converted by energy absorption into neutral atoms or molecules in the excited state, providing a selected light source for supplying of additional energy in an amount corresponding to the difference between that of the excited and that of the ionized state of the gas sample, thereby causing selective ionization of this sample and exerting an electric or magnetic force on the ions to emit them from the gas stream as stable atoms on a substrate. 30 9. A method of depositing substances, characterized in that a gas reagent in the metastable state is mixed with a gas sample, which comprises a single crystal matrix element containing a vapor phase dopant, gas sample and dopant by energy absorption 8201632 «* - 30 - in neutral atoms or molecules in the excited state, provides a selected light source for supplying additional energy in an amount corresponding to the difference between that of the excited state and that of the ionized state of gas sample and dopant, whereby selected ionization of both matrix and dopant occurs and exerts an electric or magnetic force on the ions, to simultaneously deposit them from the gas stream as stable ions on a substrate, whereby the mixed matrix-10 molecules and dopant molecules form a single crystal, which is doped in a controlled manner. A method according to claim 8 or 9, characterized in that the ions are metal ions. Process according to claim 8 or 9, characterized in that the ions are non-metal ions. 12. Method according to claim 8 or 9, characterized in that the ions are organic. Process according to claim 8 or 9, characterized in that the ions are inorganic. 14. A method according to claim 8 or 9, characterized in that the ions are polymer. Method according to claim 8 or 9, characterized in that the ions are a gas. Process according to claim 8 or 9, characterized in that the ions are allowed to deposit from the gas stream in a collection zone. Method according to claim 8 or 9, 35, characterized in, 8201632 * t - 31 - that the gas reagent is air and the gas sample is a hydrocarbon and the ions react with each other. Method according to claim 8 or 9, 5, characterized in that the ions are metal ions and are deposited on a substrate with the formation of a catalyst. 19. Process according to claim 8 or 9, characterized in that the ions are hydrocarbons and the energy supplied is sufficient for cracking the hydrocarbons into petrol and other shorter hydrocarbons. 20. Method according to claim 8 or 9, characterized in that the ions comprise at least three separable metals and two selective ionization stages are carried out with two successively selected light sources in order to obtain three separate purified metal deposits. 21. A method according to claim 8 or 9, characterized in that an electric or magnetic source is used instead of the selected light source and the gas reagent is air and the gas sample is a hydrocarbon and a combustion reaction is allowed to occur. 25 8201632 R y. d I E I -it- 25AUG1983 Improvement of errata in the description associated with patent application No. 8201632 Ned. proposed by applicant dated 24 August 1983._ On page 31, after line 24 add: Process for hydrocarbon cracking, characterized in that an improved hydrocarbon mixture is prepared by forming a metastable gas reagent and mixing it with hydrocarbon vapor to break carbon-carbon bonds in the molecules of this hydrocarbon vapor. Thü / HB J J 8201632