Plasma deposited coatings, and low temperature plasma method of making same

A method of depositing on a substrate a multiple element alloy of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition region and positioning a substrate therein;
• b. providing a plurality of feedstock gases, substantially free of chemically bonded hydrogen, at least one of said feedstock gases containing an element or elements which are components of the multiple element alloy in chemically bonded form with a reactive gasifier element, and at least another one of said feedstock gases being a multielement compound containing at least one scavenger element capable of preferentially bonding with and scavenging said reactive gasifier element;
• c. providing a source of plasma excitation energy;
• d. exciting said source of plasma excitation energy to excite the feedstock gas compounds to form in a volume in which magnetic fields present can not create an electron cyclotron reasonance condition, a plasma therein of excited precursor species, wherein said preferentially bonding scavenger element bonds with said reactive gasifier element to form a chemical compound that is carr1ied off as an effluent in the process at rates sufficient to remove reactive gasifier elements from the plasma whereby to provide net film deposition;
• and
• e. positioning at least a portion of said plasma of excited precursor species adjacent a surface of said substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species.

A method of depositing on a substrate a multiple element alloy of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition regions and positioning a substrate therein;
• b. providing a plurality of feedstock gases, substantially free of chemically bonded hydrogen, at least one of said feedstock gases containing an element or elements which are components of the multiple element alloy in chemically bonded form with a reactive gasifier element and at least another one of said feedstock gases containing at least one scavenger element capable of preferentially bonding with and scavenging said reactive gasifier element and being present in the feedstock gas in substantial stoichiometric excess to scavenge said reactive gasifier element;
• c. providing a source of plasma excitation energy;
• d. exciting said source of plasma excitation energy to excite the feedstock gas compounds to form in a volume in which magnetic field present can not create an electron resonance condition a plasma therein of excited precursor species, wherein said preferentially bonding element bonds with said reactive element to form a chemical compound that is carried off as an effluent in the process at rates sufficient to remove reactive gasifer element from the plasma whereby to provide net film deposition;
• and
• e. positioning at least a portion of said plasma of excited precursor species adjacent a surface of said substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species.

A method of depositing on a substrate a multiple element alloy of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition region and positioning a substrate therein;
• b. providing a plurality of feedstock gases, substantially free of chemically bonded hydrogen, at least one of said feedstock gases containing an element or elements which are components of the multiple element alloy in chemically bonded form with a reactive gasifier element, and at least another one of said feedstock gases being a multielement compound containing at least one scavenger element capable of preferentially bonding with and being present in the feedstock gas in substantial excess to scavenge said reactive gasifier element;
• c. providing a source of plasma excitation energy;
• d. exciting said source of plasma excitation energy to excite the feedstock gas compounds to form in a volume in which magnetic fields can not create an electron cyclotron condition a plasma therein of excited precursor species, wherein said preferentially bonding scavenger element bonds with said reactive gasifier element to form a chemical compound that is carried off as an effluent in the process at rates sufficient to remove reactive gassifier elements from the plasma whereby to provide net film deposition;
• and
• e. positioning at least a portion of said plasma of excited precursor species adjacent a surface of said substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species.

A method of depositing on a thermally degradable substrate chosen from the group consisting of organic polymeric substrates a multiple element silicon alloy of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition region and positioning the thermally degradable substrate therein;
• b. providing a plurality of feedstock gases, substantially free of chemically bonded hydrogen, one of said feedstock gases containing perfluorosilane, and another one of said feedstock gases containing a stoichiometric excess of nitrogen capable of preferentially bonding with and scavenging the fluorine, said feedstock gas containing an element capable of reacting with the silicon to form the silicon alloy;
• c. providing a microwave source of plasma excitation energy;
• d. exciting said microwave source of plasma excitation energy to excite the feedstock gas compounds to form a plasma therein of excited precursor species in the substantial absence of a magnetic field, wherein said nitrogen bonds with said fluorine to form a chemical compound that is carried off as an effluent in the process;
• and
• e. positioning a least a portion of said plasma of excited precursor species adjacent a surface of said thermally degradable substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species.

A method of depositing on a substrate a boron-carbon alloy of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition region and positioning a substrate therein;
• b. providing a plurality of feedstock gases, each containing at least one of the elements to be deposited and each being substantially free of chemically bonded hydrogen, one of said feedstock gases containing in chemically bonded form boron and fluorine, at least one of said feedstock gases containing carbon, and at least one of said feedstock gases containing nitrogen;
• c. providing a source of plasma excitation energy;
• d. exciting said source of plasma excitation energy to excite the feedstock gases to form a plasma therein of excited precursor species, wherein said nitrogen bonds with said fluorine to form NF.sub.3 that is capable of being carried off as an effluent in the process;
• and
• e. positioning at least a portion of said plasma of excited precursor species adjacent a surface of said substrate to form thereon from said excited precursor species a boron-carbon alloy film of controlled hydrogen content.

A method of depositing a substantially hydrogen free silicon oxide alloy film on an organic polymeric substrate, comprising the steps of:

• a. providing a substrate in a vacuum deposition chamber;
• b. providing a source of microwave energy;
• c. coupling the source of microwave energy to the vacuum deposition chamber;
• d. introducing a substantially hydrogen free feedstock gas composition comprising tetrafluorosilane and NO.sub.2 into the reaction chamber at a pressure corresponding substantially to a pressure minimum of a modified Paschen curve for tetrafluorosilane-NO.sub.2 reaction gas precursor composition;
• and
• e. activating the source of microwave energy and forming a plasma in the vacuum deposition chamber to deposit a substantially hydrogen free, hard, transparent silicon oxide alloy film on the organic polymeric substrate.

A method of forming a shaped article having a multiple element alloy coating on a flexible substrate, comprising the steps of:

• a. establishing vacuum deposition region and positioning the flexible substrate therein;
• b. providing a plurality of feedstock gases, substantially free of chemically bonded hydrogen, at least one of said feedstock gases containing an element or elements which are components of the multiple element alloy in chemically bonded form with a reactive gasifier element and at least another one of said feedstock gases containing at least one scavenger element capable of preferentially bonding with and scavenging said reactive gasifier element and being present in the feedstock gas in substantial excess to scavenge said reactive gasifier element;
• c. providing a microwave source of plasma energy;
• d. exciting said microwave source of plasma excitation energy and to form a plasma therein of excited precursor species in which magnetic fields present cannot create an electron cyclotron resonance condition, wherein said preferentially bonding scavenger element bonds with said reactive gasifier element to form a chemical compound that is carried off as an effluent in the process at rates sufficient to remove reactive gasifier element from the plasma whereby to provide net film deposition;
• e. positioning at least a portion of said plasma of excited precursor species adjacent a surface of said flexible substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species;
• and
• f. shaping said flexible substrate.

A method of depositing on an environmentally degradable organic polymeric substrate a multiple layer coating comprising a plurality of multiple element silicon alloy layers of controlled hydrogen content comprising the steps of:

• a. establishing a vacuum deposition region and positioning the environmentally degradable substrate therein;
• b. providing a plurality of feedstock gases, each being substantially free of chemically bonded hydrogen, a first one of said feedstock gases containing perfluorosilane, and a sequence of second feedstock gases containing a stoichiometric excess of nitrogen capable of preferentially bonding with and scavenging the fluorine, one of said second feedstock gas containing nitrogen capable of reacting with the silicon to form a silicon-nitrogen alloy and one of said second feedstock gases containing nitrogen and oxygen to form a silicon-oxygen alloy;
• c. feeding said second nitrogen containing feedstock gases in sequence to form layers of silicon-nitrogen alloy and of silicon-oxygen alloy;
• d. providing a microwave source of plasma excitation energy;
• e. forming a plasma therein of excited precursor species in the substantial absence of a magnetic field, wherein said nitrogen bonds with said fluorine to form a chemical compound that is carried off as an effluent in the process;
• and
• f. positioning a least a portion of said plasma of excited precursor species adjacent a surface of said thermally degradable substrate to form thereon from said excited precursor species an alloy film of controlled hydrogen content which includes elements derived from said precursor species.

A method of controlling the stoichiometry and properties of a plasma deposited multi-element alloy film on a substrate comprising:

• (a) forming a multi-element feedstock gas mixture, each of the elements thereof provides one or more of the following functions:
• (1) gasifying an element which will eventually comprise a component of the multi-element film on the substrate;
• (2) comprise a component of the multi-element film on the substrate;
• or
• (3) scavenging one or more of the gasifying elements;
• (b) controlling the ratio of the gasifying elements to the scavenging elements;
• (c) providing a plasma exciting energy high enough to decompose the gas component and deposit the film;
• and
• (d) controlling the relative amounts of the gasifying elements and the scavenging elements in the feedstock gas mixtures.
• so as to control the stoichiometry of the deposited film invariant of substrate temperatures and magnetic fields and deposit a multi-element alloy film.