CA1198086A - Ionization enhanced chemical process - Google Patents
Ionization enhanced chemical processInfo
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- CA1198086A CA1198086A CA000465711A CA465711A CA1198086A CA 1198086 A CA1198086 A CA 1198086A CA 000465711 A CA000465711 A CA 000465711A CA 465711 A CA465711 A CA 465711A CA 1198086 A CA1198086 A CA 1198086A
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Abstract
ABSTRACT OF DISCLOSURE
This invention relates to a new manner of carrying out chemical reactions by injection of selected forms of energy into the reaction zone by novel means. By applying this principal, many new processes result with application in a large number of different industries. The new process is generally capable of operation at room temperatures, which has advantages in the creation of certain sensitive products including uniformly doped semi-conductors, new catalysts, pure gases, high purity materials of any kind, controlled coatings, new polymers, combustion enhancement, difficult separation, petroleum refinery operations, and carrying out any reaction in which the injection of specific energy types is helpful.
This invention relates to a new manner of carrying out chemical reactions by injection of selected forms of energy into the reaction zone by novel means. By applying this principal, many new processes result with application in a large number of different industries. The new process is generally capable of operation at room temperatures, which has advantages in the creation of certain sensitive products including uniformly doped semi-conductors, new catalysts, pure gases, high purity materials of any kind, controlled coatings, new polymers, combustion enhancement, difficult separation, petroleum refinery operations, and carrying out any reaction in which the injection of specific energy types is helpful.
Description
i This invention relates to a new manner of carrying out chemical reactions by inception of selected forms of energy into the reaction zone by novel means. By applying this prin-cipal, many new pr~cesses result with application in a large number of different industries. The new process is generally capable of operation 2t room temperatures, which has advan-tages in the creation of certain sensitive products inslud-ing uniormly doped semi-conductors~ new catalysts, pure gasesl high purity matexials of any kind, controlled coat-in~s, new polymers, combustion enhancement, difficult separa-tion, petroleum refinery operations, and carrying out any re-action in which the injection of specific energy type~ is helpful.
~ particular instance is a method for producing coat-ings of selected metals, non-metals and sther molecules.
Multiple layer coatings may be formed with virtually any com bination of materials. The purity of the material of each layer may be as high as 100% and the thickness of each layer can be controlled to a single atomic or molecular layer.
Heretofore, it has been impossible to produce bodies or deposits of metals, non-metals, crystals and substances generally, and achieve a purity of approximately 100%, par-ticularly when the processes involved are carried out at ambient temperatures. Similarly, it has been found to be impossi~le to clope said bodies at ambie~t temperatures since doping has re~uired diffusion, and high temperatures have ll l been needed to permit diffusion of the dopank into the body.
For instance~ ultra pure silicon must be heated to dope it by diffusion methods. The heating, however, for this pur-pose, causes imperfections in the crystalline silicon caus-ing large numbexs of rejects.
An object of the invention is a new and improved means for carrying out a chemical process.
~ further object env.isions new and improved chemical processes involving in~ection of selected energy forms by novel means~
Another object is new and improved products created by such a process.
Still further objects will be appreciated from the fol-lowing detailed description of the invention.
The present invention comprises forming a metastable re~
agent gas, intermingling said reagent gas with a sample gas causing the latter to be energized by neutral atoms of mole-cules in an excited state, selectively ionizing said energized sample gas by introducing additional energy in an amount cor-responding to the difference between that of the excited and ionized state of said sample gas, imposing an electrical or magnetic force on said ionsto remove them from the gas stream as.stabl~ ~toms,..in a segregated.~o~,_such..~s.by depositing them on a substrate or in a container separate from the main stream of gas. The additional energy can be-added by various means~ such as a liyht source oE the laser type, or by hollow electrodes, magnetic or electric charges, or the like.
The invention has a myriad of uses for produc~ or pro-cesses in many different industries, many of which are dis~
cussed in this Application.
Referring to the invention in greater detail, it em-bodies the following principles: , 1. It is possible to generate large numbers (Ca loB
- 1014/Sec~ of so-called metastable atoms and/or molecules by passin~ neutral or ionized ground state atoms or molecules in the gas phase through a 200 to 300 volt potential. Optimum metastable production usually occurs when the reagent gas (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 atoml molecule or ion is said to be metastable when it possesses excess energy over its ground energy state and when it tends to be slow to dissipate its excess energy by radiative processes. The excess energy possessed by a meta-stable is usually transferred in part or completely during inelastic collisions.
~ particular instance is a method for producing coat-ings of selected metals, non-metals and sther molecules.
Multiple layer coatings may be formed with virtually any com bination of materials. The purity of the material of each layer may be as high as 100% and the thickness of each layer can be controlled to a single atomic or molecular layer.
Heretofore, it has been impossible to produce bodies or deposits of metals, non-metals, crystals and substances generally, and achieve a purity of approximately 100%, par-ticularly when the processes involved are carried out at ambient temperatures. Similarly, it has been found to be impossi~le to clope said bodies at ambie~t temperatures since doping has re~uired diffusion, and high temperatures have ll l been needed to permit diffusion of the dopank into the body.
For instance~ ultra pure silicon must be heated to dope it by diffusion methods. The heating, however, for this pur-pose, causes imperfections in the crystalline silicon caus-ing large numbexs of rejects.
An object of the invention is a new and improved means for carrying out a chemical process.
~ further object env.isions new and improved chemical processes involving in~ection of selected energy forms by novel means~
Another object is new and improved products created by such a process.
Still further objects will be appreciated from the fol-lowing detailed description of the invention.
The present invention comprises forming a metastable re~
agent gas, intermingling said reagent gas with a sample gas causing the latter to be energized by neutral atoms of mole-cules in an excited state, selectively ionizing said energized sample gas by introducing additional energy in an amount cor-responding to the difference between that of the excited and ionized state of said sample gas, imposing an electrical or magnetic force on said ionsto remove them from the gas stream as.stabl~ ~toms,..in a segregated.~o~,_such..~s.by depositing them on a substrate or in a container separate from the main stream of gas. The additional energy can be-added by various means~ such as a liyht source oE the laser type, or by hollow electrodes, magnetic or electric charges, or the like.
The invention has a myriad of uses for produc~ or pro-cesses in many different industries, many of which are dis~
cussed in this Application.
Referring to the invention in greater detail, it em-bodies the following principles: , 1. It is possible to generate large numbers (Ca loB
- 1014/Sec~ of so-called metastable atoms and/or molecules by passin~ neutral or ionized ground state atoms or molecules in the gas phase through a 200 to 300 volt potential. Optimum metastable production usually occurs when the reagent gas (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 atoml molecule or ion is said to be metastable when it possesses excess energy over its ground energy state and when it tends to be slow to dissipate its excess energy by radiative processes. The excess energy possessed by a meta-stable is usually transferred in part or completely during inelastic collisions.
2. Due to the relati~ely long life time of metastables, they can be easily brought into contact with metal, non-metal or moleculars in the gas phase so that through inelastic col-lisions the excess energy of the metastable reagent gas is '~J
transferred to the~. The metal, non-metal and/or molecule~
thu~ energized may become: a neutral atom or molecule in the excited stat~ or an ioniæed sp~cies.
transferred to the~. The metal, non-metal and/or molecule~
thu~ energized may become: a neutral atom or molecule in the excited stat~ or an ioniæed sp~cies.
3. Neutral atoms or molecules in excited states (i.e.
with excess energy~ may be fur~her excited to the point where an electron is eject~d (thus forming the a omic ox molecular ion) by supplying--mur~-energy in-an amount cor-responding to the energy difference betwaen the ioni~.ed and excited states of the specie~ of interest. It is often the case that the energy difference is small and can be sup plied by a light source Isuch as a dye laser etcO) that emit~ in the ultra-violet and visible portion of the electro magnetic spectrum. ~hat is, by irradiating a collection a nPutral atoms or mole~ules in the same excited state (i.e.
the same amount o exce~s energy) with monochromatic radi-ation whose Pnergy çorresponds exactly to the energy dif-ference between the excit2d and ionized states, only those atoms or molecules will be ioni ~ed .
Becau~e of the u~iqueness of the energy difference between an excited state of a particular atom or molecule and its ionized sta'ce, nearly absolute selectivity i5 achieved.
It is often the case that the energy differenoe referred to above can be altered by usin~ a different reagent gas because each reagent gas is composed of metastable atoms or molecules whos~ energy i~ different iErom one reagent gas to another.
Fox example, the characteristic meta.stable energy for some selected reagent gases is as follows helium (23S) 19.7eV, argon ~33Po 2) 11.7 eV and nitrogen (3~ ~) 6.1 eV. An added degree o~ selectivity can be attai.ned by using a re agent gas whose metastable energy differs fr~mthe ionization energy of the metal~ non-metal or molecule of interest by an amount such that ionization of any other m~terial b~t that of interest is not possiblel
with excess energy~ may be fur~her excited to the point where an electron is eject~d (thus forming the a omic ox molecular ion) by supplying--mur~-energy in-an amount cor-responding to the energy difference betwaen the ioni~.ed and excited states of the specie~ of interest. It is often the case that the energy difference is small and can be sup plied by a light source Isuch as a dye laser etcO) that emit~ in the ultra-violet and visible portion of the electro magnetic spectrum. ~hat is, by irradiating a collection a nPutral atoms or mole~ules in the same excited state (i.e.
the same amount o exce~s energy) with monochromatic radi-ation whose Pnergy çorresponds exactly to the energy dif-ference between the excit2d and ionized states, only those atoms or molecules will be ioni ~ed .
Becau~e of the u~iqueness of the energy difference between an excited state of a particular atom or molecule and its ionized sta'ce, nearly absolute selectivity i5 achieved.
It is often the case that the energy differenoe referred to above can be altered by usin~ a different reagent gas because each reagent gas is composed of metastable atoms or molecules whos~ energy i~ different iErom one reagent gas to another.
Fox example, the characteristic meta.stable energy for some selected reagent gases is as follows helium (23S) 19.7eV, argon ~33Po 2) 11.7 eV and nitrogen (3~ ~) 6.1 eV. An added degree o~ selectivity can be attai.ned by using a re agent gas whose metastable energy differs fr~mthe ionization energy of the metal~ non-metal or molecule of interest by an amount such that ionization of any other m~terial b~t that of interest is not possiblel
4. Ion~ thus produced are charged particles (by defini-tion) and therefore can ~e caus~ to mo~e in a particular de-sired dixection and accumulate, as a thin9 uniform film, at a particular desired location by imposition of an electric or magn-e~-i-~ fiel~. Fu~thel~L~r~-~y proper-sei~tion--of-the ~h-ap-e of the imposed field, mass discrimination can be achieved although it is rarely necessary with this technique.
In summary, the invention is described as follows:
a flow of argon (2000 u mQle~/run) is established in a soft vacuum (1-5 torr). The argon ~PO 2)metastable states 11.7 eY
is generated in large quantities 10 - 10 3~sec. as the argon is passed through two annular electrodes across which 200 -300 Vdc is applied. Thes~ arg~n metastable atoms reerred to as the reagent gas are brought into contact with a molecule of interest referred to as the sample gas (i.e. W(C0)6~ Ni~C0)6 silanes, perfluoro butane, etc~ where the argon metasta~le reagent gas txansfers its excess energy to the sample gas.
Many complex reactions proceed in such an energy rich en-vironm~t, however, a dominant one is the formation of the metal, ~on-metal or molecule in a neutral, high energy state and still in the gas phase. The output fxom a nitrogen~laser~
pumped pulsed tunable dye laser/set to the wavelength cor responding to the exact energy necessary to cause .ionization of the sample gas given the energy of its neutral high energy state. The conf.iguration of thP cavity or container in which the above occurs is ~uch that an electric or magnetic field can be applied so as to couple the site of formation of the ions of intexest to the site of their deposition wi~hout entraining o~er non-ionic products present in the reac~
tion zone. The layers thus deposited on a suitable target.
may be controlled in thicknes~ to an atomic or molecular layer by oontroling the rate at which sample ions are formed~ Layers of known uniform ~hickness o~ metals, non~
metals and ~lec~lles -c:an-be-~le~ited in--any-~rder thu~; -giving ~Isandwich~ type layers.
Alternativelyt two or more metals could be deposited .
simultaneously thus forming an "alloy" like layer. Or other molecules such as monomers can be deposited as ions on a sur :Eace such that polymerization occurs. And certain chemical reaction 3cno~to proceed by way of an ion can be caused at a specifi c location and at a ~pecific controlled rate.
The invention may be more readily understood by re-ferring ~o the followi~g det~iled examples:
Five examples of ~he foregoing process will be pre-sented~ The first will deal with the non-metal silicon and the second with the metal tungsten.
Example 1 By passing a 2000 micromole/minute flowing stream of Helium gas past electrodes across which 200 vdc are impos~d, from 108 to 10 4 metastable Helium atoms (in the 23S state~
are foxmed. If a vol~tilesilicon oompound such as sila~e is mixed into the stream of Helium metastable atoms, by a collisional process, the metastable energy is ~ransfer.red to the ~ilane forming neutxal ~ilicon atoms in the excited state. The difference in energy between the excited neutral atom and khe ionic form of the atom is 3 . lB eV which is equi~alent to the energy of li~ht whose wave len~th is 390.53 nanometers (nm). T~us if light whose wavelength is 390 ~ 53 nm is incident on the neutral exclted silicon atoms~ they will absorb the incident light and in doing so b~come~ionized. By imposing eithex ~n electric or magnet.ic field gradient between the ions and a suitable target, the ions and ~nly the ions, will migrate to the target where they take on an electron ~nd are deposited uniformly as ground state neutral atoms.
Example 2 As for the example dealing with a metal, tungsten will be considered. The same procedure (as desc~ibed above in the case of silicon) is u~ed for the metal tungsten. The volatile tung5ten compound used is tungsten hexacarbonyl WlCO)6~ Neutral excited tungsten ~toms are-formed in a man-ner similar to that for silicon. The difference in energy between the neutral excited tungsten atom a~d its ionic form is 2.54 eV which is eguivalent to the energy of light whose w~ve~ength is 489.73 nm. Thus, if light whose wavelength is 489.73 nm i's incident on the neutral excited tungsten atoms, they will absorb the inciden~ light alld in doing so become ion-ized. As before, an electric or magnetic field gradient will cause the migration of the ion~ to the target where they pick up an electron and are deposited uniformly on the target ~ur~
face a5 neutral tun~sten atom$ in the ground state, Table 1 summarizes the energy relationship de5cribed or referred to above~ ~
~ Any suitable target may be used, whether it be metal; non-m~tal, inorganic or organic substances. ~ suit-abl~ exampl-e target~~or examples 1 and 2 is a quartz pl-ate].
Example 3 P-N JUNCTION -- PHOTOVOLTAIC CELL
The following example is a principle application of the invention.
Photo~oltaic cells used as a means of generating elec-tric power have aome under intense investigation in recent years due to the necessity of generatin~ electric power in remote places ~uch as spaceO In the past, use of photovol-taic cell or power production has be~n very expensive (i.e.
up to $175,000/kilowatt). The high cost cited was the re-sult of the necessity of employing very complicated and cost-ly fabrication procedures so that-the device-could be-made at all. Even so, the rejection rate was as great as 30~. With interest in photovoltaic cells expanding to i~clude commer cial use to provide a power source alternative to fossil fu-els, any reduction in cost of producing photovoltaic cell would further aurrent yoalsO
The example discussed below will consider a photovolta-ic cell based on a silicon matrix where the P layer is sili-con doped with antimony and arsenic or phosphorous. The P and N layers are formed so that a sandwich configuration results~
TAB~E 1 A nm Rcal . eV K cal eV
Ncsn-me~al Si~ 2506 . 9 250 . 69 ' 114 .1 4 . 95 Si 15~6~8 152.~8 ~87.3 ~.12 energv difference 3905 O 3 39t3 53 ____O_ ?3 ~ 2 ~ t be~w~n exci~ed neutral a~om and it~ ionized ~orm ~.8 al W 4008.8 400.~ 71.3 3.09 ~
, ;~
W 220~.5 220.5 1~9.7 5.63 energy difference 4897 . 3 389 0 7 ~ 58 ~ 4 - 2 ~ 54 between exc~ ted neut~al ~ tQm and it ionized form It will be appreciated that the application of the principle of the i~vention will produce P-N 3unction devices ~photovoltaic cells, etc.) in a mannex tha~: ~
1) is c~rried out at ambient koo~ temperatures and thus eliminates the use of the high temperature induction furnaces presently required hy current processes, 2) the doping process is carried out continuously and in a preci~ely controlled manner at ambient temperaturesresulting in concentrations of do-pan at the bottom of the silicon layer that is equal to that ound at any other depth in the layer, and thus eliminates the normal non-?inear difusion of the dopant as a function of depth that always re~ults from ~he high temperature diffusion process currently used~
3) permits ~he formation of a P-N junction de~ice with layer thickness, dopant type and dopant con-centration controlled remotely so that the sub-strate, (the surface to which the photovoltaic cell is connected) once mounted, is not handled or otherwise physically removed from the apparatus employed for the deposition of the P-N junc~ion ma~erial.
In this example, for illustrative purposes, the N dopant will be boron and ~he P d~p~l~
will be antimony and phosphorou~. Because these dopants were selected it i~ not implied that other dopants could not ~e em-ployed in exactly the same manner, that is, by the application of the principle of the invention. This example differs fro~ the previous one a~ follows: in the previous example the manner in which a metal or non metal could be purified to very high levels of purity was pre~ented; .however in the ex~mple be-low~ the means by which a controlled amount of a specific impurity and no other can be incorporated into a high purity matrix where the 2mount of ~pecific impurity may be very ~mall, is discussed~ ~down to parts per 100 trillion).
The source of silicon is lpicked from ~he wide variety and larqe number of volatil~ silicon compounds such a5 tetra methyl silicQn.- The-~volatile--compounds are--~elect~d -be~ause ~hey have high vapor pressures or readily form gases at room temperature An amount of the silicon compound e~uivalent to one or twv grams of silicon is placed in a closed vessel that can:
1) have its ~emperature controlled to within + O.Ol~C
from 100C to -200C, 2) be connected to a manifold through a metering valve.
The valve is initially closed so that the gas-solid in the vessel can be brought into thermal equilibrium with the vessel. The temperature controller is adj~sted to the tem-perature that will result in the desired pressure for the gaseous silicon compound, tetra methyl silicon (TMS), for ex~
ample 27C will re~ult in a gaseous rrMs pressure of approxi-mately 150 mm o.E Hg.
The souroe of boron i5 picked from a large number of boron containing compounds, such as the hydrides and diborane, that are volati.le. The volatile compounds are selected because they ha~e high vapox pressures or readily form gases at room temperature. An amount of diborane e~uivalent to one or two milligrams of boron is placed in a closed vessel with charac-teristics similar to the vessel containing the silicon com-pound; and the boron containing vessel is connected~to he same manifold so that tha two gases can be mixed as requiredO
~ecause the amount of dopant is usually very small, parts per billion or less, relative to the silicon, the low temperature capabilities of the boron containing vessel must be employed.
That is by mainkaining the temperature at approximately 165C
a vapor pressure of approximately 1 to 2 mm of Hg resultsr Therefore, if the twv gases d TMS and diborane were allowed to mix freely in the manifold at their respective vapor pres-sures, the diborane would be approximately 1 parts per tril lion with respect to TMS. In order to reduce the concentra-tion of diborane further it is useful ko use the metering valves that separate each vessel from the manifold and apply in a soft vacuum to the manifold. In ~is way arbitrarily 1GW
concentrations of borane can be achieved in the flowing mix~
ture of ~he two gases. The soft vacuum applied to the mani-fold provides the driving force or mean~ to transfer the gas mixtures to other locations within the apparatus.
As above (i.e. in the previous example) a gas such as helium ~s selected for the purpose of forming a reac~ant gasO
It will ~e recalled that by passing approximately 2 mols/
minute of ~elium through a conduit such as glass tubing that at some convenient point has two annular electrodes around the outer surface of the conduit separated by 3 to 5 centi-meter with 200 Vdc imposed across them, energetic or excited neutral atoms of helium will be formedO These neutral excited atoms are referred to as the metastable gas or reactant gasO
1~
J~
The manifold into which the ~MS and borane gases are allowed to flow is connected to the glass tubing ox conduit in which the metastable gas is formed in such a way~that the TMS ana borane gas mixture 10ws into the metastable ~as where ener~y is transferre~ from the metastable atoms ~neutral excited atoms~ to TMS and diboraneO This configuratlon is ~elected (instead of the one in which both the TMS and di-borane ga~ mixture and the helium mix prior to the fQrmation of the reactant or metastable gas) so that silicon and boron ion~ are not form~d prior to irradiation with light whose wavelength~s~ correspond~s) to ener~y(ies) equal to that (those) required to ionize silicon and boron from their neutral excited states. The reason being that by avoiding indiscriminate ioni-z~tion very high purity levels can be aehieved as well as high coatin~ rates. It is noted, however, that under some circum-stances it might be useful to form ions of either the dopant or silicon by mixing with the helium prior to the formation of the metastable gas - namely when; the need or desire to eliminate the use of one light source such as a laser exists, and~or lo~er standards of purity can be tolerated but higher coating rates necessaryO However, in this example that case shall not be considered in detail. In either case though, when energy is transferred Erom the metastable gas to the TMS
and diborane, the excited neutral silicon and boron atoms are foxmed. Table 2 summarizes the energy conte~t of the most prominent excited neutral states and ionized states of sili-con, borcn, phosphcrous, antimony and arsenic. Included in the table are the various energy differences b~tween the ex-cited neutral iand ionized states of the elements mentioned.
At th.is point, the gas containing the neutral excited ~ilicon and boron can be passed through an electric ~nd/or magnctio field in order to re ve unwanted ions that may be formed during energy transfer from the metastable gas, such as impurities whose io~ization energy is less than silicon and boron. This procedure results in very high purity of the gas stream. In fact in order to achieve the highest purity a gas such a5 helium is selected because of its large ener-gy content in the metastable state approximately 21 eV, thus causing efficient ionization of impurities (with low i.oniza~
tion energy and inefficient ionization of atoms or molecules with high ionization energies.) The gas containing the silicon and ~oron atoms in their excited neutral states, is then irradiated by intense light from a source ~uch a~ a hollow cathode lamp or a laser ~tunable dye type for example). The light should be mono chromatic (or nearly so) with a wavelength of 3247.774 Angstroms (A) or 3.818 electron volts ~eV). Either a single pass or mul-tiple pass confiyuration of the light path through the gas can be employed depending on: the intrinsic intensity of the li~ht source and the concentration of neutral excited ~ilicon and ~ro~ atoms. A multiple pass optical configuration is preferred.
When the neutral excited silicon and boron absorb light of this wavelength the respective ions are formed because light whose wavelength is 3247.774 A meets the ionization energy requir~ments of silicon in its most long lived neutral state and exceeds that required by boron in its most long lived neutral state.
The iOllS thus formed whila still in th~ moving gas stream are passed ~hrough an electric a~d/or magnetic field and the ions are diverted from the stream (by theix interaction with the field) I'able 2 Element ~ S ate Energy r)ifference State Energy between neu~ral li ioniæed state~
O O
A eV eV A
Matrix Silicon;
neutral 2881.578 4 . 303 ionized 1533 . 55û 8 3. ~18 3247 . 77 P Layer Dopant Boron:
neutral 2497.733 4.965 ionized 1362.460 8.296 3 . 331 ~ 3722 . 606 N Layer Dopan ~s Arltimony:
neutral 2060 . 380 5 . 995 ionized 1435.351 8.639 3 . ~44 3~2 . 854 Phosphorous:
eutral 2534 . 010 4 0 893 ionized 1182.75510.484
In summary, the invention is described as follows:
a flow of argon (2000 u mQle~/run) is established in a soft vacuum (1-5 torr). The argon ~PO 2)metastable states 11.7 eY
is generated in large quantities 10 - 10 3~sec. as the argon is passed through two annular electrodes across which 200 -300 Vdc is applied. Thes~ arg~n metastable atoms reerred to as the reagent gas are brought into contact with a molecule of interest referred to as the sample gas (i.e. W(C0)6~ Ni~C0)6 silanes, perfluoro butane, etc~ where the argon metasta~le reagent gas txansfers its excess energy to the sample gas.
Many complex reactions proceed in such an energy rich en-vironm~t, however, a dominant one is the formation of the metal, ~on-metal or molecule in a neutral, high energy state and still in the gas phase. The output fxom a nitrogen~laser~
pumped pulsed tunable dye laser/set to the wavelength cor responding to the exact energy necessary to cause .ionization of the sample gas given the energy of its neutral high energy state. The conf.iguration of thP cavity or container in which the above occurs is ~uch that an electric or magnetic field can be applied so as to couple the site of formation of the ions of intexest to the site of their deposition wi~hout entraining o~er non-ionic products present in the reac~
tion zone. The layers thus deposited on a suitable target.
may be controlled in thicknes~ to an atomic or molecular layer by oontroling the rate at which sample ions are formed~ Layers of known uniform ~hickness o~ metals, non~
metals and ~lec~lles -c:an-be-~le~ited in--any-~rder thu~; -giving ~Isandwich~ type layers.
Alternativelyt two or more metals could be deposited .
simultaneously thus forming an "alloy" like layer. Or other molecules such as monomers can be deposited as ions on a sur :Eace such that polymerization occurs. And certain chemical reaction 3cno~to proceed by way of an ion can be caused at a specifi c location and at a ~pecific controlled rate.
The invention may be more readily understood by re-ferring ~o the followi~g det~iled examples:
Five examples of ~he foregoing process will be pre-sented~ The first will deal with the non-metal silicon and the second with the metal tungsten.
Example 1 By passing a 2000 micromole/minute flowing stream of Helium gas past electrodes across which 200 vdc are impos~d, from 108 to 10 4 metastable Helium atoms (in the 23S state~
are foxmed. If a vol~tilesilicon oompound such as sila~e is mixed into the stream of Helium metastable atoms, by a collisional process, the metastable energy is ~ransfer.red to the ~ilane forming neutxal ~ilicon atoms in the excited state. The difference in energy between the excited neutral atom and khe ionic form of the atom is 3 . lB eV which is equi~alent to the energy of li~ht whose wave len~th is 390.53 nanometers (nm). T~us if light whose wavelength is 390 ~ 53 nm is incident on the neutral exclted silicon atoms~ they will absorb the incident light and in doing so b~come~ionized. By imposing eithex ~n electric or magnet.ic field gradient between the ions and a suitable target, the ions and ~nly the ions, will migrate to the target where they take on an electron ~nd are deposited uniformly as ground state neutral atoms.
Example 2 As for the example dealing with a metal, tungsten will be considered. The same procedure (as desc~ibed above in the case of silicon) is u~ed for the metal tungsten. The volatile tung5ten compound used is tungsten hexacarbonyl WlCO)6~ Neutral excited tungsten ~toms are-formed in a man-ner similar to that for silicon. The difference in energy between the neutral excited tungsten atom a~d its ionic form is 2.54 eV which is eguivalent to the energy of light whose w~ve~ength is 489.73 nm. Thus, if light whose wavelength is 489.73 nm i's incident on the neutral excited tungsten atoms, they will absorb the inciden~ light alld in doing so become ion-ized. As before, an electric or magnetic field gradient will cause the migration of the ion~ to the target where they pick up an electron and are deposited uniformly on the target ~ur~
face a5 neutral tun~sten atom$ in the ground state, Table 1 summarizes the energy relationship de5cribed or referred to above~ ~
~ Any suitable target may be used, whether it be metal; non-m~tal, inorganic or organic substances. ~ suit-abl~ exampl-e target~~or examples 1 and 2 is a quartz pl-ate].
Example 3 P-N JUNCTION -- PHOTOVOLTAIC CELL
The following example is a principle application of the invention.
Photo~oltaic cells used as a means of generating elec-tric power have aome under intense investigation in recent years due to the necessity of generatin~ electric power in remote places ~uch as spaceO In the past, use of photovol-taic cell or power production has be~n very expensive (i.e.
up to $175,000/kilowatt). The high cost cited was the re-sult of the necessity of employing very complicated and cost-ly fabrication procedures so that-the device-could be-made at all. Even so, the rejection rate was as great as 30~. With interest in photovoltaic cells expanding to i~clude commer cial use to provide a power source alternative to fossil fu-els, any reduction in cost of producing photovoltaic cell would further aurrent yoalsO
The example discussed below will consider a photovolta-ic cell based on a silicon matrix where the P layer is sili-con doped with antimony and arsenic or phosphorous. The P and N layers are formed so that a sandwich configuration results~
TAB~E 1 A nm Rcal . eV K cal eV
Ncsn-me~al Si~ 2506 . 9 250 . 69 ' 114 .1 4 . 95 Si 15~6~8 152.~8 ~87.3 ~.12 energv difference 3905 O 3 39t3 53 ____O_ ?3 ~ 2 ~ t be~w~n exci~ed neutral a~om and it~ ionized ~orm ~.8 al W 4008.8 400.~ 71.3 3.09 ~
, ;~
W 220~.5 220.5 1~9.7 5.63 energy difference 4897 . 3 389 0 7 ~ 58 ~ 4 - 2 ~ 54 between exc~ ted neut~al ~ tQm and it ionized form It will be appreciated that the application of the principle of the i~vention will produce P-N 3unction devices ~photovoltaic cells, etc.) in a mannex tha~: ~
1) is c~rried out at ambient koo~ temperatures and thus eliminates the use of the high temperature induction furnaces presently required hy current processes, 2) the doping process is carried out continuously and in a preci~ely controlled manner at ambient temperaturesresulting in concentrations of do-pan at the bottom of the silicon layer that is equal to that ound at any other depth in the layer, and thus eliminates the normal non-?inear difusion of the dopant as a function of depth that always re~ults from ~he high temperature diffusion process currently used~
3) permits ~he formation of a P-N junction de~ice with layer thickness, dopant type and dopant con-centration controlled remotely so that the sub-strate, (the surface to which the photovoltaic cell is connected) once mounted, is not handled or otherwise physically removed from the apparatus employed for the deposition of the P-N junc~ion ma~erial.
In this example, for illustrative purposes, the N dopant will be boron and ~he P d~p~l~
will be antimony and phosphorou~. Because these dopants were selected it i~ not implied that other dopants could not ~e em-ployed in exactly the same manner, that is, by the application of the principle of the invention. This example differs fro~ the previous one a~ follows: in the previous example the manner in which a metal or non metal could be purified to very high levels of purity was pre~ented; .however in the ex~mple be-low~ the means by which a controlled amount of a specific impurity and no other can be incorporated into a high purity matrix where the 2mount of ~pecific impurity may be very ~mall, is discussed~ ~down to parts per 100 trillion).
The source of silicon is lpicked from ~he wide variety and larqe number of volatil~ silicon compounds such a5 tetra methyl silicQn.- The-~volatile--compounds are--~elect~d -be~ause ~hey have high vapor pressures or readily form gases at room temperature An amount of the silicon compound e~uivalent to one or twv grams of silicon is placed in a closed vessel that can:
1) have its ~emperature controlled to within + O.Ol~C
from 100C to -200C, 2) be connected to a manifold through a metering valve.
The valve is initially closed so that the gas-solid in the vessel can be brought into thermal equilibrium with the vessel. The temperature controller is adj~sted to the tem-perature that will result in the desired pressure for the gaseous silicon compound, tetra methyl silicon (TMS), for ex~
ample 27C will re~ult in a gaseous rrMs pressure of approxi-mately 150 mm o.E Hg.
The souroe of boron i5 picked from a large number of boron containing compounds, such as the hydrides and diborane, that are volati.le. The volatile compounds are selected because they ha~e high vapox pressures or readily form gases at room temperature. An amount of diborane e~uivalent to one or two milligrams of boron is placed in a closed vessel with charac-teristics similar to the vessel containing the silicon com-pound; and the boron containing vessel is connected~to he same manifold so that tha two gases can be mixed as requiredO
~ecause the amount of dopant is usually very small, parts per billion or less, relative to the silicon, the low temperature capabilities of the boron containing vessel must be employed.
That is by mainkaining the temperature at approximately 165C
a vapor pressure of approximately 1 to 2 mm of Hg resultsr Therefore, if the twv gases d TMS and diborane were allowed to mix freely in the manifold at their respective vapor pres-sures, the diborane would be approximately 1 parts per tril lion with respect to TMS. In order to reduce the concentra-tion of diborane further it is useful ko use the metering valves that separate each vessel from the manifold and apply in a soft vacuum to the manifold. In ~is way arbitrarily 1GW
concentrations of borane can be achieved in the flowing mix~
ture of ~he two gases. The soft vacuum applied to the mani-fold provides the driving force or mean~ to transfer the gas mixtures to other locations within the apparatus.
As above (i.e. in the previous example) a gas such as helium ~s selected for the purpose of forming a reac~ant gasO
It will ~e recalled that by passing approximately 2 mols/
minute of ~elium through a conduit such as glass tubing that at some convenient point has two annular electrodes around the outer surface of the conduit separated by 3 to 5 centi-meter with 200 Vdc imposed across them, energetic or excited neutral atoms of helium will be formedO These neutral excited atoms are referred to as the metastable gas or reactant gasO
1~
J~
The manifold into which the ~MS and borane gases are allowed to flow is connected to the glass tubing ox conduit in which the metastable gas is formed in such a way~that the TMS ana borane gas mixture 10ws into the metastable ~as where ener~y is transferre~ from the metastable atoms ~neutral excited atoms~ to TMS and diboraneO This configuratlon is ~elected (instead of the one in which both the TMS and di-borane ga~ mixture and the helium mix prior to the fQrmation of the reactant or metastable gas) so that silicon and boron ion~ are not form~d prior to irradiation with light whose wavelength~s~ correspond~s) to ener~y(ies) equal to that (those) required to ionize silicon and boron from their neutral excited states. The reason being that by avoiding indiscriminate ioni-z~tion very high purity levels can be aehieved as well as high coatin~ rates. It is noted, however, that under some circum-stances it might be useful to form ions of either the dopant or silicon by mixing with the helium prior to the formation of the metastable gas - namely when; the need or desire to eliminate the use of one light source such as a laser exists, and~or lo~er standards of purity can be tolerated but higher coating rates necessaryO However, in this example that case shall not be considered in detail. In either case though, when energy is transferred Erom the metastable gas to the TMS
and diborane, the excited neutral silicon and boron atoms are foxmed. Table 2 summarizes the energy conte~t of the most prominent excited neutral states and ionized states of sili-con, borcn, phosphcrous, antimony and arsenic. Included in the table are the various energy differences b~tween the ex-cited neutral iand ionized states of the elements mentioned.
At th.is point, the gas containing the neutral excited ~ilicon and boron can be passed through an electric ~nd/or magnctio field in order to re ve unwanted ions that may be formed during energy transfer from the metastable gas, such as impurities whose io~ization energy is less than silicon and boron. This procedure results in very high purity of the gas stream. In fact in order to achieve the highest purity a gas such a5 helium is selected because of its large ener-gy content in the metastable state approximately 21 eV, thus causing efficient ionization of impurities (with low i.oniza~
tion energy and inefficient ionization of atoms or molecules with high ionization energies.) The gas containing the silicon and ~oron atoms in their excited neutral states, is then irradiated by intense light from a source ~uch a~ a hollow cathode lamp or a laser ~tunable dye type for example). The light should be mono chromatic (or nearly so) with a wavelength of 3247.774 Angstroms (A) or 3.818 electron volts ~eV). Either a single pass or mul-tiple pass confiyuration of the light path through the gas can be employed depending on: the intrinsic intensity of the li~ht source and the concentration of neutral excited ~ilicon and ~ro~ atoms. A multiple pass optical configuration is preferred.
When the neutral excited silicon and boron absorb light of this wavelength the respective ions are formed because light whose wavelength is 3247.774 A meets the ionization energy requir~ments of silicon in its most long lived neutral state and exceeds that required by boron in its most long lived neutral state.
The iOllS thus formed whila still in th~ moving gas stream are passed ~hrough an electric a~d/or magnetic field and the ions are diverted from the stream (by theix interaction with the field) I'able 2 Element ~ S ate Energy r)ifference State Energy between neu~ral li ioniæed state~
O O
A eV eV A
Matrix Silicon;
neutral 2881.578 4 . 303 ionized 1533 . 55û 8 3. ~18 3247 . 77 P Layer Dopant Boron:
neutral 2497.733 4.965 ionized 1362.460 8.296 3 . 331 ~ 3722 . 606 N Layer Dopan ~s Arltimony:
neutral 2060 . 380 5 . 995 ionized 1435.351 8.639 3 . ~44 3~2 . 854 Phosphorous:
eutral 2534 . 010 4 0 893 ionized 1182.75510.484
5 . 5gl 221~ . 021 Arsenic -neutral 1890.5006.559 ioni2ed 1264 . 010 9 . 810 3 . 251 3814 . 211 and directed thereby to a suitable surface for coating.
If further purification is required of the gas stream prior to the point at which ~ilicon and boron ions ar~ form~d ~namely when irradiated with monochroma~ic light whose wave-length is 3247.774 A~; then the gas stream can be first irra-diated with monochromatic light whose wavelength i5 slightly O
less than 3722.61 A. By doing so, an~ undesixable atomic or molecular species that can be ionized by 3722.61 A light will be and can be removed from the gas stream by passing it through an el~ctric and/ox magnetic field located between O
the 372~.61 A and 3247.774 A light sources.
The ions, ~ilicon and boron, are deposited on a nega-tively ch~rged target where they form a crystal or crystals while picking up an electron and thus become neutral in a crys-tal lattice. The deposition process may proceed for as long as necessary to achieve the desired thickness.
Once the desired thickness ~f P layer has been deposited, the N layer i5 deposited on top of the P layer withou~ the neces-~ity of removing the substrate-P layer for inspection or poiish-ing. Any one or combination of the N layer dopants can be used in ~urming the N layer with silicon as the matrix. The method and apparatus employed is exactly the same as that described for forming the P layer u~ing boron except ~hat the wavelength of light used to orm the ions is selected ~o correspond to the energ~ difference between the neutral excited and ionized sta~es o the particular atoms being u~ed.
One further refinement that is useful in producing the ~Xi~ll~ purity of a particular atomic species is worth mention-ing. Thou~h a particular atom, silicon r is used for illustra-tive it will be appreciated that the refin ment could be applied __ . _ .. .. _ ...... . . .. . .
to any other atom as well, e.g. germani~un, etc.
Once the silicon atom is formed in its excited neutral state other neutral excited atoms, of an unwanted sox~ an also be formed. If the~e contaminant ats:>ms can be ionized by 3247.774 A light then th~y carl be ionized along with ~he sili-con. Therefbre by irradiating all of the neutral excited atoms with anolther monochromatic light source whose wavelength s~orres-ponds to an energy slightly less than that requixed ~or the neutral exsilted silioGn ~toms to be ionized ~3250 A) neut.ral excited silicorl atc)ms will proceed with the gas stream un-changed but the other neutral excited atoms that can be ion-ized will be and can be diverted out o:f the gas stream by ap-plication of an electric and/or magnetic field. It is also clear that any other neutral excited atoms as well as silicon will continue on with the gas stream that when the monochro-matic l~ght 3247.774 A irradiates the stream only the neutral excited silicon atoms will be i~nized and all other atoms will pass on with the gas stream. Thus the refinement under discus-sion provides an energy filter of approximately 3 A such that those neutral excited atoms that can be ionized at energies lower than neutral excited silicon are ioni~ed and those neu-tral excited atoms that require more energy to become ioni.zed than neutral excited silicon never became ionized and pass on with the gas stream to waste or collection.
Four additional examples of the appl.ication of metastable gases ~o useul processes are presented below, namely:
1~ two laser metal purification application 2~ combustion application 3) catalyst formation 4) hydxocarbon cracklng Example 3 Metal Purification with l~o Lasers A summaxy of this use can be briefly stated as follows:
a gas such as helium is passed through an electric field such that a large concentration of the excited neutral form of helium is created, referred to as metastable helium atoms; a volatile form of a selected metal, non-metal or other molecule referred to as the reactant yas i5 introduced into the stream of helium metastable atoms whereby energy transfer from the metastable atoms to the ~eactant gas atoms/molecules occurs, thus in-creasing the energy of the reactant molecules/atoms to an energy state referred to as a neutral excited state (th~ energy of which is less than that xequired to cause ionization of the reactant gas atoms/molecules; by irradiation of the neutral excited reactant gas atoms/molecules with light whose wave-length corresponds exactly to the energy difference between the excited neutral reactant species and the ionized reac~ant species, ionization occurs for those species in the reactan~
gas for which the sum of the metastable energy and the energy of the irradiation light equals or exceeds the ionization ener-gy. Thus any i.mpurity species in the reactant gas whose ion-ization energy requirement exceeds this sum will not be ion-ized and is therefore eliminatecl as a candidate for deposition in a thin film since deposition in this invention depends on ions. It is al.so clear that impurity species in the reactant .
gas whose ionization energy is less than this sum will be ionized along with the reactant and subsequently deposited in the thin film, and is thus regarded as an impurity. By reorga~izing the method of application of this invention to the deposition films and extending the idea upon which the invention is based t it is possible to avoid the inclusion in the thin film of impurity sp cies whose ioni%ation energy requirement is less ~han or equal to the reactant species. The discussion below illus-trates the method for a mixture of nickel t iron and tungsten where the objective is to make a thin film of nickel but one with no inclusions of iron or tungsten. Ref~rring to Table 1 and bearing in mind the details of the invention, it is clear that once the m~tastable reactant gas of nickel has been formed along wi~ those of the impurities, iron and tunqsten, irradiation with 6316.9A light will cause the ionization of the nickel and iron neutral excited species but will not cause ionization of the tungsten neutral excited species.
Table 1 Neutral O IonizedO Difference O
Excited (~ State (Ae~ in Energy i~
W 4008.8 ~204.5 48g7.3 (Tungsten)3.093eV 5.625eV 2.532eV
O O O
Fe 3581.2A 2382.OA 7114.2A
(Iron)3.463eV 5.206eV 1.743eV
O O O
Ni 3414.8A 2216.~A 6316.9A
(Nickel)3~631eV 5.594eV 1.963eV
Thus, after deposition the nickel thin film will be found to in-clude only one of the two impurity species, that is iron but no~
tungsten. If, however, the neutral excited reactant specie and impurity species are first irradiated with light whose wave-length is greater than 6316.gA the impurity species iron will be ioniæed but none of the rest. The iron ions can then be diverted, ~electrically or magnetically, from the reactant gas species ~the nickel) and the only re~in;ng impurity species, (that is the tungsten). The remaining mixture is then irradi-ated with light whose wavelength is less than or equal to 6316.9A but greater than 4897.3A thus forming nickel ions but not tungsten ions. In this way a reactant species whose ioAization energy requirement is intermediate or between those of two im-purity species can be separated and deposited as a thin film free ~rom inclusions of impurities.
In actual form the process would be run as follows:
By passing a 2 millmole/minute stream of helium, enclosed in a glass conduit~ through two annular electrodes across which 300 Vdc is applied approximately 1014 metastable helium atoms per second are formed. The reactant gas (composed of gaseous reactant Ni (CO)6 ~nickel carbonyl) and two impurities Fe(CO)6 and W(CO)6, iron carbonyl and tungsten carbonyl respecti~ely) is introduced into the helium metastable stream and mixed by turbulence and diffusion. The neutral excited states of each metal is formed by collisi~nal energy transfer and/or Foster processes and helium is left in its neutral ground state. The reactant gas stream now containing the neutxal excited species iron, nickel and tungsten, is conducted by pressure difference along the glass conduit to a point at which it is irradiated by light whose wavelength is greater than 6316.9A
(say 6500A) wh,ereupon the iron neutral excited species are ion-ized but not the nickel and tunysten neutral excited species.
The ionized iron is attracted to a negatively charged target within the glass conduit and thereby eliminated from the re actant gas. The reactant gas str2am now containing the neu-tral excited specieC nickel and tungsten only is conducted by pressure difference further along the glass conduit to a point at which it is irradiated by light whose wavelength is less than or equal to 6316.9A but not less than or equal to 4897~3A
whereupon the nickel neutral exci~ed species are ionized but not the tungsten neutral excited species. The ionized nickel is at-tracted to another negatively charged tar~et within the glass conduit where it is deposited and forms a layer of nickel free from iron and tungsten, because the iron was previously eliminated as described above and the tungsten was never ionized and as such not deposited with the nickel.
Example 4 Enhanced Combustion of Hydrocarbon Fuels With this discussion we shall present an example of a new means by which the metastable gases nitrogen and oxygen can be employed to improve the efficiency with which hydrocarbon fuels can be burned. The efficiency of combustion is related to the amount of useful work that can be extracted from the combustion products. In the absence of the process/means to be described, an internal combustion engine uses 15 parts of aix for every part of fuel; however, when the means to be described i5 employed with the internal combustion engine 33 parts of air for every part of fuel are consumed. Thus the efficiency of combustion is in-creased by a factor of 2.2.
The new means of combusting hydrocarbon Fuels provides for:
1) the production of more useful work per unit mass of fuel than current combustion methods 2) more complete combustion of fuel and therefore lower levels of polluting or harmful gases (i.~NO, N02, CO, etc.) in the exhaust 3) the elimination of the need for costly pollution abatement equipment in automobiles 4) more cost effective use of fuel ~ he new means of combustion on the fuel-oxidant mixture (i.e,02 in air~ being passed through an electrostatic or mag-ne ie field created by applying a DC voltage across two axially aligned annular electrodes that surround the channel through which the gas mixture passes on its way to the combustion cham~
ber. The resulting gas mixture has a high concentration of "metastable" oxygen and nitrogen molecules. Because ~he phy~
sical nature of metastable atoms and/or molecules has been ex-plained above, no further discussion of their physical nature will be presented; however, it is worth noting that the meta-stable atoms and/or molecules are not ions/ hence the process does not depend on ionization or a plasma.
When metastable energy is collisionally transferred from either oxygen or nitrogen or both, to gas phase fuel and/or fuel aerosol (as a droplet) the increase in energy results in a reduction in the "activation energy" for combustion in the case of the vapor phase fuel molecules and an increase in vapor pressure of the fuel in the fuel aerosol particles. The last observation flows from the fact that liquid phase fuel does not burn but rather vapor phase fuel does burn. Thus in the case where the fuel is not well vapoxized (i.e. in an aerosol), a sub-stantial amount of heat derived from the combustion of gas phase fuel~
is required to supply the heat of vaporization for the fuel droplets in the aerosol~ The heat used to vaporize fuel droplets cannot be converted into work. When a fuel droplet in the aerosol receives addit~onal energy such aæ collisionally transferred metastable energy an increase in the vapor pressure of the ~uel aerosol droplet occurs due to the well accepted and widely used prin-ciple of thermodynamic equilibrium. Any open chemical system i5 con~tantly seeking the state of thermodynamic equilibrium because it i~ by definition the most stable state. Thermody-namic equilibrium is achieved by the re-distribution of excess energy into the electronic, translational, vibrational and ro-tational energy modes of the open chemical ~ystem. Thus if metastable energy is added to an aerosol fuel droplet it enters into the electronic mode of the system,but as the system tends to thermodynamic equilibrium, the excess electronic energy is quickly (Ca 10 6 sec) redistributed into the translational vibrational and rotational modes. These are the energy modes that most influence the vapor pressure of the fuel droplet, in descending order of importance.
It is hy both the reduction of the activation energy of combustion for gas phase ~uel molecules and the increase in vapor pressure of the aerosol fuel droplets that the 2.2 factor increase in combust~n efficiency is achieved.
The pxactical embodiment of this use is described in terms of an internal combustion 4-cycle engine, as in an automobile.
The fuel air mixture used therein is conducted to each cylinder by the intake manifold. Opposite each intake port, to which the intake manifold is connected mechanically, a conventional air-tight electrical feed-through is located on said manifold. The electrical feed-throu~h is insulated from the manifold. A one millimeter diameter metal rod is welded to the electrical connector on the inside of the manifold. The length of the rod is adjusted so that it does not interfere with the operation of the valve. The metal of the rod is seleeted to have a high electronic work func-tion and to be inert. Tantalum was used in this example. Tothe exterior portion of the electrical conne~tor, a positive connection to a 300 volt D.C. power supply is attached. The nega-~ive connector of the power supply is attached to the metal of the manifold. This completes the electrical circuit which includes the air gap between the tantalum metal rod and the interior metal surface of the manifold through which the hydrocarbon fuel-air mixture 10ws during operation. The power supply was selected to operate on a 12 volt D.C. input and to deliver 300 volts D.C.
output at 10 watts of power.
As a result of this operation, increased power and de-creased deleterious exhaust causes resulted, the exhaust gas being largely carbon dioxide and water vapor.
Example 5 Catalyst Fabrication Many industrial processes rely on catalysts such as the metals platinum, rhodium, silver, nickel~ gold, ironO copper, zinc and others. Even alloys of some of these metals are used as catalysts. Even though any or all of the above catalysts could-be formed-by--the-method to-be-~escribe~-only the-platinum catalyst will be considered in connection with the ammonia oxida-tion process for the forma~ion of nitric acid.
A platinum gauze is u~ed as the catalyst in the ammonia oxidation industrial process. The majority of the mass of the platinum gau2e is provided to assure a mechanically stable phy-sical structure and a large surface-area. Due to the expense of the metal il would be desirable to produce a platinum coat-ing on a much less expensive mechanical support.
Ordinarily, a catalyst i5 not consumed during the course of the reaction it initiates. However, in the case of the platinum gauze used in the ammonia oxidation process, the platinum appears to be consumed! The reason this occurs is that ~ .
impurities in the platinum gauze react with ammonia or nitrous oxide or nitric acid but the platinum does notO The result is the physical ero~ion of the platinum gauze which leads to its disintegration and the need to replace it with fresh gauze.
Thus if ultrapure platinum could be coated on to a mechanically stable high surface area substrate such as aluminum oxide (A1203), the catalyst would last indefinitely and be vastly less expensive. The process described below achieves that end.
The method employed is exactly the same as that described in item 3 above. However, the volatile form of platinum may be platinum hexafluoride (PtF5) or Pt ~PF3)4. The first light irradiation source would have a wavelength greater than 2858.8A
which would eliminate all impurities whose ionization energy requirement ~as less than that of platinum. The second light ir radiation source would have a wavelength less than or equal to O O
2858.8A although no more than lOOA less, which will cause the ionization of the platinum neutral excited species and no others.
The~second target could be A1203 or quartz wool towhich a nega-tive static charge is applied. r~hus the platinum ions would be neutralized and simultaneously deposited onto the substrate building up a surface of desired thickness and of virtually 100% purity. The amount of platinum required would be 0.001%
the mass of that required for the conventional platinum gauze catalyst and last 10 to 100 times longer. E le 6 By means of this example we will describe a new use relat-ing tv the production of petroleum products such as gasoline~ jet fuel, fue~ oil and the like frcm crude oil by a means not requir-ing a catalyst. Currently the case is that substantial amounts ~ J
o~ costly cracking catalyst are required to produce petroleum products ~rom crude oil in the majority of oil refining pro-cesses. The useful life-time of cracking catalysts ranges from a few hours to weeks, depen~ing on ~he quality and chemi-cal characteristics of the crude oil being refined. Further, the cost of a fresh catalyst charge for a medium size oil re~
finery can be as high as $400,000 r according to Jim Hatten of the Tex~s Eastern Co. Thus it i.s clear that a new means of carrying out crude oil cracking that does not require an expensive catalyst could reduce production costs and there-fore the consumer costs.
A brief description of the process is as follows:
So-called "cracking" of hydrocarbons is a non~technical way of referring or designating the rupture of a carbon-carbon bond in the hydrocarbon. The tendency of any chemical bond~
such as a carbon-carbon bond~ to precist can be expressed in terms of bond energy. Thus, in order to cause the rupture of such a bond requires at least the applica~ion of an acceptable form of energy to the bond to be ruptured and in an amount adequate to cause the desired rupture. Catalysts have been successfully put to this problem. Thus, catalysts have the means of reducing the tendency of the carbon-carbon bond to persist to the point or extent rupture occurs. Hence, catalyst "cracking" of crude oil to yield petroleum products can be thought of as a process whereby long chain hydrocarbons (crude oil) is broken up into short chain hy-drocarbons (petroleum products) ~y means of a catalyst that causes the rupture of carbon-carbon bond in long chain hydro-carbons. The resulting mixture is then distilled in the normal or conventional way.
The new invention does not require catalyst use; however, ~_.
a new means of providing the required energy for carbon-carbon bond rupture is central to the process. The energy source used i5 a metastable form of one or more of the fixed gases or inert gases such as nitrogen, argon, helium, neon~ krypton. Because o~ the abundance of nitrogen, i~ is considered to be the pre-ferred choice although the other gases work as well.
~ metastable gas molecule or atom is one that has ex-cess energy in an amount sufficient to produce an excited state that is "metastable", i.e., relatively long lived (0010 millisec~
onds). When a large collection o metastable gas molecules ex-ist they are referred to as a metastable gas. When ~ch a gas i5 brought in contact, that is mixed, with hydrocarbons colli-sion between the hydrocarbon molecules and metastable molecules/
atoms to the hydrocarbon molecules, the metastable species men-tioned above all have sufficient energy to rupture the carbon-carbon bond in the host hydrocarbon molecule. The fate of the metastable gas molecule after energy transfer is that it returns to the yround state li-e-, state of minimum electronic, vibra-tional and rotational energy). Metastable gases are generated by passing a stream of ground state gas molecules/atoms through a DC potential gradient or by ~xposing the gas stream to a micro-wave field.
More specificallyt in order to break a carbon carbon chemical or covalent bond homolytically 84~4 Kcal per mol must be applied to the hydrocarbon. This ~mount of energy corresponds to 3.66 eV. The metastable energy of certain fixed and inert gases i5 shown in the table below.
Table I
Atom/ Spectroscopy Metastable Molecule Notation Energy in eV
He 2 S 20.6 23~ 19.82 Ne 3pO 16.7 3P2 16.6 Ar 3pO 11.7 3P2 11.5 ~r 3pO 10.5 3P2 9.9 Xe 3P1 8.43 2(g~ 3~ 6.03 Thus by passing nitrogen gas through an annular pair of electrodes across which 200 volts DC is applied or through a microwave generator or magnetic field substantial amounts of metastable species of nitrogen are produced. The amount per unit time of metastable gas produced depends on the power applied to thP electrical field or magnetic field or microwave field, as well AS the flow rate of the ground state gas through the electro-magnetic force (EMF) field. For examplel a 200 VDC 5 watt EMF
f.ield i.5 ade~uate to produce S X 1023 metastable atoms/molecules per 10 min. Because the production of metastable atoms/molecules is physically sim:ilar to an optical absorption process which de-pends on instantaneous concentration of ground state gas in the 2~
field, scale-up is readily feasible. Thus, petroleum products are formed at a rate equal to that of the production of metastable gas molecules dimin;shed by losses to the walls and recombination pro-cesses. The estimated loss is less than lO~I
With crude oil in the vapor phase such as the flllidized ~ed cracker combination with a metastable gas of the type described above, it is straightforward, where a 50-50 ratio of metastable gas to crude oil vapor is maintained by means of concentric an-nular jets.
Experimental evidence of the principle was obtained using a long chain hydrvcarbon, n-decane. When n-decane vapor was mixed with nitroyen gas metastable molecules by means of a con-centric annular jet the following products were obtained:
Table II
Carbon ~ Relative %
l-6 41 7 4.3 8 13.4 9 10.7 l~ 6.7 ll 13.
a) includes isomers Thus it :is cleax hydrocarbon cracking can be promoted as described.
`3 Other ~referred applications envisoned for this inven-tion are~
1) catalyst metals deposited on inexpensive substrates.
2~ microelectronic units or components (diodes, trans-istors and the like) 3) metal or polymer coatings to retard or prohibit cor-xosion ~nd~or wear 41 special optical surfaces and crystals 5) low cost conductors
If further purification is required of the gas stream prior to the point at which ~ilicon and boron ions ar~ form~d ~namely when irradiated with monochroma~ic light whose wave-length is 3247.774 A~; then the gas stream can be first irra-diated with monochromatic light whose wavelength i5 slightly O
less than 3722.61 A. By doing so, an~ undesixable atomic or molecular species that can be ionized by 3722.61 A light will be and can be removed from the gas stream by passing it through an el~ctric and/ox magnetic field located between O
the 372~.61 A and 3247.774 A light sources.
The ions, ~ilicon and boron, are deposited on a nega-tively ch~rged target where they form a crystal or crystals while picking up an electron and thus become neutral in a crys-tal lattice. The deposition process may proceed for as long as necessary to achieve the desired thickness.
Once the desired thickness ~f P layer has been deposited, the N layer i5 deposited on top of the P layer withou~ the neces-~ity of removing the substrate-P layer for inspection or poiish-ing. Any one or combination of the N layer dopants can be used in ~urming the N layer with silicon as the matrix. The method and apparatus employed is exactly the same as that described for forming the P layer u~ing boron except ~hat the wavelength of light used to orm the ions is selected ~o correspond to the energ~ difference between the neutral excited and ionized sta~es o the particular atoms being u~ed.
One further refinement that is useful in producing the ~Xi~ll~ purity of a particular atomic species is worth mention-ing. Thou~h a particular atom, silicon r is used for illustra-tive it will be appreciated that the refin ment could be applied __ . _ .. .. _ ...... . . .. . .
to any other atom as well, e.g. germani~un, etc.
Once the silicon atom is formed in its excited neutral state other neutral excited atoms, of an unwanted sox~ an also be formed. If the~e contaminant ats:>ms can be ionized by 3247.774 A light then th~y carl be ionized along with ~he sili-con. Therefbre by irradiating all of the neutral excited atoms with anolther monochromatic light source whose wavelength s~orres-ponds to an energy slightly less than that requixed ~or the neutral exsilted silioGn ~toms to be ionized ~3250 A) neut.ral excited silicorl atc)ms will proceed with the gas stream un-changed but the other neutral excited atoms that can be ion-ized will be and can be diverted out o:f the gas stream by ap-plication of an electric and/or magnetic field. It is also clear that any other neutral excited atoms as well as silicon will continue on with the gas stream that when the monochro-matic l~ght 3247.774 A irradiates the stream only the neutral excited silicon atoms will be i~nized and all other atoms will pass on with the gas stream. Thus the refinement under discus-sion provides an energy filter of approximately 3 A such that those neutral excited atoms that can be ionized at energies lower than neutral excited silicon are ioni~ed and those neu-tral excited atoms that require more energy to become ioni.zed than neutral excited silicon never became ionized and pass on with the gas stream to waste or collection.
Four additional examples of the appl.ication of metastable gases ~o useul processes are presented below, namely:
1~ two laser metal purification application 2~ combustion application 3) catalyst formation 4) hydxocarbon cracklng Example 3 Metal Purification with l~o Lasers A summaxy of this use can be briefly stated as follows:
a gas such as helium is passed through an electric field such that a large concentration of the excited neutral form of helium is created, referred to as metastable helium atoms; a volatile form of a selected metal, non-metal or other molecule referred to as the reactant yas i5 introduced into the stream of helium metastable atoms whereby energy transfer from the metastable atoms to the ~eactant gas atoms/molecules occurs, thus in-creasing the energy of the reactant molecules/atoms to an energy state referred to as a neutral excited state (th~ energy of which is less than that xequired to cause ionization of the reactant gas atoms/molecules; by irradiation of the neutral excited reactant gas atoms/molecules with light whose wave-length corresponds exactly to the energy difference between the excited neutral reactant species and the ionized reac~ant species, ionization occurs for those species in the reactan~
gas for which the sum of the metastable energy and the energy of the irradiation light equals or exceeds the ionization ener-gy. Thus any i.mpurity species in the reactant gas whose ion-ization energy requirement exceeds this sum will not be ion-ized and is therefore eliminatecl as a candidate for deposition in a thin film since deposition in this invention depends on ions. It is al.so clear that impurity species in the reactant .
gas whose ionization energy is less than this sum will be ionized along with the reactant and subsequently deposited in the thin film, and is thus regarded as an impurity. By reorga~izing the method of application of this invention to the deposition films and extending the idea upon which the invention is based t it is possible to avoid the inclusion in the thin film of impurity sp cies whose ioni%ation energy requirement is less ~han or equal to the reactant species. The discussion below illus-trates the method for a mixture of nickel t iron and tungsten where the objective is to make a thin film of nickel but one with no inclusions of iron or tungsten. Ref~rring to Table 1 and bearing in mind the details of the invention, it is clear that once the m~tastable reactant gas of nickel has been formed along wi~ those of the impurities, iron and tunqsten, irradiation with 6316.9A light will cause the ionization of the nickel and iron neutral excited species but will not cause ionization of the tungsten neutral excited species.
Table 1 Neutral O IonizedO Difference O
Excited (~ State (Ae~ in Energy i~
W 4008.8 ~204.5 48g7.3 (Tungsten)3.093eV 5.625eV 2.532eV
O O O
Fe 3581.2A 2382.OA 7114.2A
(Iron)3.463eV 5.206eV 1.743eV
O O O
Ni 3414.8A 2216.~A 6316.9A
(Nickel)3~631eV 5.594eV 1.963eV
Thus, after deposition the nickel thin film will be found to in-clude only one of the two impurity species, that is iron but no~
tungsten. If, however, the neutral excited reactant specie and impurity species are first irradiated with light whose wave-length is greater than 6316.gA the impurity species iron will be ioniæed but none of the rest. The iron ions can then be diverted, ~electrically or magnetically, from the reactant gas species ~the nickel) and the only re~in;ng impurity species, (that is the tungsten). The remaining mixture is then irradi-ated with light whose wavelength is less than or equal to 6316.9A but greater than 4897.3A thus forming nickel ions but not tungsten ions. In this way a reactant species whose ioAization energy requirement is intermediate or between those of two im-purity species can be separated and deposited as a thin film free ~rom inclusions of impurities.
In actual form the process would be run as follows:
By passing a 2 millmole/minute stream of helium, enclosed in a glass conduit~ through two annular electrodes across which 300 Vdc is applied approximately 1014 metastable helium atoms per second are formed. The reactant gas (composed of gaseous reactant Ni (CO)6 ~nickel carbonyl) and two impurities Fe(CO)6 and W(CO)6, iron carbonyl and tungsten carbonyl respecti~ely) is introduced into the helium metastable stream and mixed by turbulence and diffusion. The neutral excited states of each metal is formed by collisi~nal energy transfer and/or Foster processes and helium is left in its neutral ground state. The reactant gas stream now containing the neutxal excited species iron, nickel and tungsten, is conducted by pressure difference along the glass conduit to a point at which it is irradiated by light whose wavelength is greater than 6316.9A
(say 6500A) wh,ereupon the iron neutral excited species are ion-ized but not the nickel and tunysten neutral excited species.
The ionized iron is attracted to a negatively charged target within the glass conduit and thereby eliminated from the re actant gas. The reactant gas str2am now containing the neu-tral excited specieC nickel and tungsten only is conducted by pressure difference further along the glass conduit to a point at which it is irradiated by light whose wavelength is less than or equal to 6316.9A but not less than or equal to 4897~3A
whereupon the nickel neutral exci~ed species are ionized but not the tungsten neutral excited species. The ionized nickel is at-tracted to another negatively charged tar~et within the glass conduit where it is deposited and forms a layer of nickel free from iron and tungsten, because the iron was previously eliminated as described above and the tungsten was never ionized and as such not deposited with the nickel.
Example 4 Enhanced Combustion of Hydrocarbon Fuels With this discussion we shall present an example of a new means by which the metastable gases nitrogen and oxygen can be employed to improve the efficiency with which hydrocarbon fuels can be burned. The efficiency of combustion is related to the amount of useful work that can be extracted from the combustion products. In the absence of the process/means to be described, an internal combustion engine uses 15 parts of aix for every part of fuel; however, when the means to be described i5 employed with the internal combustion engine 33 parts of air for every part of fuel are consumed. Thus the efficiency of combustion is in-creased by a factor of 2.2.
The new means of combusting hydrocarbon Fuels provides for:
1) the production of more useful work per unit mass of fuel than current combustion methods 2) more complete combustion of fuel and therefore lower levels of polluting or harmful gases (i.~NO, N02, CO, etc.) in the exhaust 3) the elimination of the need for costly pollution abatement equipment in automobiles 4) more cost effective use of fuel ~ he new means of combustion on the fuel-oxidant mixture (i.e,02 in air~ being passed through an electrostatic or mag-ne ie field created by applying a DC voltage across two axially aligned annular electrodes that surround the channel through which the gas mixture passes on its way to the combustion cham~
ber. The resulting gas mixture has a high concentration of "metastable" oxygen and nitrogen molecules. Because ~he phy~
sical nature of metastable atoms and/or molecules has been ex-plained above, no further discussion of their physical nature will be presented; however, it is worth noting that the meta-stable atoms and/or molecules are not ions/ hence the process does not depend on ionization or a plasma.
When metastable energy is collisionally transferred from either oxygen or nitrogen or both, to gas phase fuel and/or fuel aerosol (as a droplet) the increase in energy results in a reduction in the "activation energy" for combustion in the case of the vapor phase fuel molecules and an increase in vapor pressure of the fuel in the fuel aerosol particles. The last observation flows from the fact that liquid phase fuel does not burn but rather vapor phase fuel does burn. Thus in the case where the fuel is not well vapoxized (i.e. in an aerosol), a sub-stantial amount of heat derived from the combustion of gas phase fuel~
is required to supply the heat of vaporization for the fuel droplets in the aerosol~ The heat used to vaporize fuel droplets cannot be converted into work. When a fuel droplet in the aerosol receives addit~onal energy such aæ collisionally transferred metastable energy an increase in the vapor pressure of the ~uel aerosol droplet occurs due to the well accepted and widely used prin-ciple of thermodynamic equilibrium. Any open chemical system i5 con~tantly seeking the state of thermodynamic equilibrium because it i~ by definition the most stable state. Thermody-namic equilibrium is achieved by the re-distribution of excess energy into the electronic, translational, vibrational and ro-tational energy modes of the open chemical ~ystem. Thus if metastable energy is added to an aerosol fuel droplet it enters into the electronic mode of the system,but as the system tends to thermodynamic equilibrium, the excess electronic energy is quickly (Ca 10 6 sec) redistributed into the translational vibrational and rotational modes. These are the energy modes that most influence the vapor pressure of the fuel droplet, in descending order of importance.
It is hy both the reduction of the activation energy of combustion for gas phase ~uel molecules and the increase in vapor pressure of the aerosol fuel droplets that the 2.2 factor increase in combust~n efficiency is achieved.
The pxactical embodiment of this use is described in terms of an internal combustion 4-cycle engine, as in an automobile.
The fuel air mixture used therein is conducted to each cylinder by the intake manifold. Opposite each intake port, to which the intake manifold is connected mechanically, a conventional air-tight electrical feed-through is located on said manifold. The electrical feed-throu~h is insulated from the manifold. A one millimeter diameter metal rod is welded to the electrical connector on the inside of the manifold. The length of the rod is adjusted so that it does not interfere with the operation of the valve. The metal of the rod is seleeted to have a high electronic work func-tion and to be inert. Tantalum was used in this example. Tothe exterior portion of the electrical conne~tor, a positive connection to a 300 volt D.C. power supply is attached. The nega-~ive connector of the power supply is attached to the metal of the manifold. This completes the electrical circuit which includes the air gap between the tantalum metal rod and the interior metal surface of the manifold through which the hydrocarbon fuel-air mixture 10ws during operation. The power supply was selected to operate on a 12 volt D.C. input and to deliver 300 volts D.C.
output at 10 watts of power.
As a result of this operation, increased power and de-creased deleterious exhaust causes resulted, the exhaust gas being largely carbon dioxide and water vapor.
Example 5 Catalyst Fabrication Many industrial processes rely on catalysts such as the metals platinum, rhodium, silver, nickel~ gold, ironO copper, zinc and others. Even alloys of some of these metals are used as catalysts. Even though any or all of the above catalysts could-be formed-by--the-method to-be-~escribe~-only the-platinum catalyst will be considered in connection with the ammonia oxida-tion process for the forma~ion of nitric acid.
A platinum gauze is u~ed as the catalyst in the ammonia oxidation industrial process. The majority of the mass of the platinum gau2e is provided to assure a mechanically stable phy-sical structure and a large surface-area. Due to the expense of the metal il would be desirable to produce a platinum coat-ing on a much less expensive mechanical support.
Ordinarily, a catalyst i5 not consumed during the course of the reaction it initiates. However, in the case of the platinum gauze used in the ammonia oxidation process, the platinum appears to be consumed! The reason this occurs is that ~ .
impurities in the platinum gauze react with ammonia or nitrous oxide or nitric acid but the platinum does notO The result is the physical ero~ion of the platinum gauze which leads to its disintegration and the need to replace it with fresh gauze.
Thus if ultrapure platinum could be coated on to a mechanically stable high surface area substrate such as aluminum oxide (A1203), the catalyst would last indefinitely and be vastly less expensive. The process described below achieves that end.
The method employed is exactly the same as that described in item 3 above. However, the volatile form of platinum may be platinum hexafluoride (PtF5) or Pt ~PF3)4. The first light irradiation source would have a wavelength greater than 2858.8A
which would eliminate all impurities whose ionization energy requirement ~as less than that of platinum. The second light ir radiation source would have a wavelength less than or equal to O O
2858.8A although no more than lOOA less, which will cause the ionization of the platinum neutral excited species and no others.
The~second target could be A1203 or quartz wool towhich a nega-tive static charge is applied. r~hus the platinum ions would be neutralized and simultaneously deposited onto the substrate building up a surface of desired thickness and of virtually 100% purity. The amount of platinum required would be 0.001%
the mass of that required for the conventional platinum gauze catalyst and last 10 to 100 times longer. E le 6 By means of this example we will describe a new use relat-ing tv the production of petroleum products such as gasoline~ jet fuel, fue~ oil and the like frcm crude oil by a means not requir-ing a catalyst. Currently the case is that substantial amounts ~ J
o~ costly cracking catalyst are required to produce petroleum products ~rom crude oil in the majority of oil refining pro-cesses. The useful life-time of cracking catalysts ranges from a few hours to weeks, depen~ing on ~he quality and chemi-cal characteristics of the crude oil being refined. Further, the cost of a fresh catalyst charge for a medium size oil re~
finery can be as high as $400,000 r according to Jim Hatten of the Tex~s Eastern Co. Thus it i.s clear that a new means of carrying out crude oil cracking that does not require an expensive catalyst could reduce production costs and there-fore the consumer costs.
A brief description of the process is as follows:
So-called "cracking" of hydrocarbons is a non~technical way of referring or designating the rupture of a carbon-carbon bond in the hydrocarbon. The tendency of any chemical bond~
such as a carbon-carbon bond~ to precist can be expressed in terms of bond energy. Thus, in order to cause the rupture of such a bond requires at least the applica~ion of an acceptable form of energy to the bond to be ruptured and in an amount adequate to cause the desired rupture. Catalysts have been successfully put to this problem. Thus, catalysts have the means of reducing the tendency of the carbon-carbon bond to persist to the point or extent rupture occurs. Hence, catalyst "cracking" of crude oil to yield petroleum products can be thought of as a process whereby long chain hydrocarbons (crude oil) is broken up into short chain hy-drocarbons (petroleum products) ~y means of a catalyst that causes the rupture of carbon-carbon bond in long chain hydro-carbons. The resulting mixture is then distilled in the normal or conventional way.
The new invention does not require catalyst use; however, ~_.
a new means of providing the required energy for carbon-carbon bond rupture is central to the process. The energy source used i5 a metastable form of one or more of the fixed gases or inert gases such as nitrogen, argon, helium, neon~ krypton. Because o~ the abundance of nitrogen, i~ is considered to be the pre-ferred choice although the other gases work as well.
~ metastable gas molecule or atom is one that has ex-cess energy in an amount sufficient to produce an excited state that is "metastable", i.e., relatively long lived (0010 millisec~
onds). When a large collection o metastable gas molecules ex-ist they are referred to as a metastable gas. When ~ch a gas i5 brought in contact, that is mixed, with hydrocarbons colli-sion between the hydrocarbon molecules and metastable molecules/
atoms to the hydrocarbon molecules, the metastable species men-tioned above all have sufficient energy to rupture the carbon-carbon bond in the host hydrocarbon molecule. The fate of the metastable gas molecule after energy transfer is that it returns to the yround state li-e-, state of minimum electronic, vibra-tional and rotational energy). Metastable gases are generated by passing a stream of ground state gas molecules/atoms through a DC potential gradient or by ~xposing the gas stream to a micro-wave field.
More specificallyt in order to break a carbon carbon chemical or covalent bond homolytically 84~4 Kcal per mol must be applied to the hydrocarbon. This ~mount of energy corresponds to 3.66 eV. The metastable energy of certain fixed and inert gases i5 shown in the table below.
Table I
Atom/ Spectroscopy Metastable Molecule Notation Energy in eV
He 2 S 20.6 23~ 19.82 Ne 3pO 16.7 3P2 16.6 Ar 3pO 11.7 3P2 11.5 ~r 3pO 10.5 3P2 9.9 Xe 3P1 8.43 2(g~ 3~ 6.03 Thus by passing nitrogen gas through an annular pair of electrodes across which 200 volts DC is applied or through a microwave generator or magnetic field substantial amounts of metastable species of nitrogen are produced. The amount per unit time of metastable gas produced depends on the power applied to thP electrical field or magnetic field or microwave field, as well AS the flow rate of the ground state gas through the electro-magnetic force (EMF) field. For examplel a 200 VDC 5 watt EMF
f.ield i.5 ade~uate to produce S X 1023 metastable atoms/molecules per 10 min. Because the production of metastable atoms/molecules is physically sim:ilar to an optical absorption process which de-pends on instantaneous concentration of ground state gas in the 2~
field, scale-up is readily feasible. Thus, petroleum products are formed at a rate equal to that of the production of metastable gas molecules dimin;shed by losses to the walls and recombination pro-cesses. The estimated loss is less than lO~I
With crude oil in the vapor phase such as the flllidized ~ed cracker combination with a metastable gas of the type described above, it is straightforward, where a 50-50 ratio of metastable gas to crude oil vapor is maintained by means of concentric an-nular jets.
Experimental evidence of the principle was obtained using a long chain hydrvcarbon, n-decane. When n-decane vapor was mixed with nitroyen gas metastable molecules by means of a con-centric annular jet the following products were obtained:
Table II
Carbon ~ Relative %
l-6 41 7 4.3 8 13.4 9 10.7 l~ 6.7 ll 13.
a) includes isomers Thus it :is cleax hydrocarbon cracking can be promoted as described.
`3 Other ~referred applications envisoned for this inven-tion are~
1) catalyst metals deposited on inexpensive substrates.
2~ microelectronic units or components (diodes, trans-istors and the like) 3) metal or polymer coatings to retard or prohibit cor-xosion ~nd~or wear 41 special optical surfaces and crystals 5) low cost conductors
6~ high purity materials of any kind
7) to replace any high temperature epitaxial process
8) to separate in relatively pure form any difficultly separable elements/ including but not limited to the rare earth elements, metals of the platinum group, rare gases such as argonl neon, etc., hydrogen, helium or other gases, atmos-pheric gases generally, and the halogens
9~ to carry out any chemical reaction in which the injection of specific energy types is helpful.
Although many variations may be contemplated within the scope of the invention we intend to be limited only by the fol-lowing Patent Claims.
29a
Although many variations may be contemplated within the scope of the invention we intend to be limited only by the fol-lowing Patent Claims.
29a
Claims
1. The process for cracking hydrocarbons which comprises forming a metastable reagent gas, inter-mingling the same with hydrocarbon vapor, to cause the rupture of carbon-to-carbon bonds in the molecules of said hydrocarbon vapor to produce an improved hydrocarbon mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/213,039 US4335160A (en) | 1978-11-21 | 1980-12-04 | Chemical process |
| CA000399807A CA1181361A (en) | 1980-12-04 | 1982-03-30 | Ionization enhanced chemical process |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399807A Division CA1181361A (en) | 1980-12-04 | 1982-03-30 | Ionization enhanced chemical process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198086A true CA1198086A (en) | 1985-12-17 |
Family
ID=25669632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000465711A Expired CA1198086A (en) | 1980-12-04 | 1984-10-17 | Ionization enhanced chemical process |
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| Country | Link |
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| CA (1) | CA1198086A (en) |
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1984
- 1984-10-17 CA CA000465711A patent/CA1198086A/en not_active Expired
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