TW201120232A - Deposition of alkaline earth metal fluoride films in gas phase at low temperature - Google Patents

Abstract

Disclosed are thermal and/or plasma-enhanced CVD, ALD, and/or pulse CVD processes to deposit alkaline earth metal fluoride-based films, such as MgF2, at temperatures ranging from about 25 DEG C to about 300 DEG C, preferably from about 50 DEG C to about 250 DEG C, and more preferably from about 100 DEG C to about 200 DEG C.

Description

201120232 VI. Description of invention: [Reference to the relevant application] This application is based on 35U.SC § 119(e) claiming the interest of the provisional application No. 61/265,130 applied for on May 30, 2009, The application is hereby incorporated by reference in its entirety. [Technical Field to Which the Invention Is Applicable] The disclosure is for use in a range from about 25. (: a film mainly composed of an alkaline earth metal fluoride, such as MgF2, is deposited at a temperature of about 30 (TC, preferably about 50 C to about 25 Torr, and more preferably about 1 〇 crc to about 2 〇 crc) / or plasma enhanced CVD, ALD, and / or pulsed c VD method. [Prior Art] Anti-refraction layer (ARL) or coating (ARC) is important in many processes, such as optical coatings. It has been used in complementary metal oxide semiconductor (CMOS) image sensor processes. The CM〇s image sensor (cis) is a charge-coupled detector (CCD) replacement for photosensor applications. An anti-refraction coating is deposited over the image sensor on top of the microlens. The coating protects the microlens and increases the sensitivity of the cis. The coating must have a low refractive index of microlenses that are more likely to be made of Si〇2. In this case, the Arc requires a refractive index of < 1 46. Certain low dielectric constant (1 〇 wk) materials used in many electronic component processes also exhibit a low refractive index, which allows them to be used as a coating. Layer. However, sometimes the use of UV hardening treatment is required to improve film properties and this step is at 201120232. Layer cause harm.

MgF2 has an RI of 丨.35 (at 4 〇〇 nm) and does not require a uv hardening step. Magnesium-containing films have been deposited using ALD (see, for example, US Pat. App. pub_ No. 2008/210973). However, in the 卞 application, magnesium acts as a dopant in the zinc oxide film. This reference does not disclose whether the method can produce a MgF2 film that meets the requirements.

One problem encountered with MgFz film deposition is impurities, such as the bonding of other metals or oxygen. Mg0 has a refractive index of # i 7 , resulting in an excessively high refractive index. ~ There is still a need for a deposition method for an oral metal fluoride film at temperatures below about 3 ,, preferably below 25 (TC, and more preferably below (9) 。. Marking and naming methods, the following description and The full text of the patent scope uses a specific abbreviation, the symbol / = includes the term "r-alkyl" refers to the saturation of only carbon and hydrogen atoms; b-base is another procedure, "burning" refers to straight chain, branched chain or ring Examples of the home-based linear alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, etc. Examples of the branched alkyl group include, but are not limited to, a tertiary butyl group. The cycloalkyl group, examples include but not限%工# 铱propyl, cyclopentyl, cyclohexyl, etc. ^ Department ^ methyl, abbreviation "Et" means ethyl; abbreviation "p] means propyl; abbreviation "i P,, injury lFr Buckling of isopropyl; abbreviation Bu" means butyl (n-butyl); shrinking ",, 〆 difficult to write tBu means tertiary butyl; abbreviation "sBu" ^ means secondary butyl; abbreviation acac means acetyl Acetylacetonato, abbreviated as "tmhd, ' ^ ib ? 9 曰 2,2,6,6-tetramethyl-3,5-heptanedionate; P (10)0) 'abbreviation 〇d' means 2,4_xin Diketo acid group (octadionato:

S 4 201120232 The abbreviation mhd means 2-mercapto-3,5-hexanedione acid group (hexadinonato); and the term tm〇d" means 2,2,6,6_tetradecyl_3,5_ The octyl ketone acid group; the abbreviation lbpm refers to the 2,2,6-trimethyl-3-5-heptanedione group; the abbreviation "hfac" is the 曰', the fluorine * hexafluoroacetylacetonato The abbreviated aC system is difluoroacetylacetonato; the abbreviation Cp refers to cyclopentadienyl; the abbreviation "cp*, 'refers to pentadecylcyclopentadienyl' abbreviated dkti' refers to diketone Diketimine (regardless of the R ligand attached to the nitrogen atom): the abbreviation "emk" refers to the enaminone (the enammoketones H regardless of the R-coordination of the nitrogen atom); the abbreviation amd refers to the sulfhydryl group ( Amidinate) (whether or not the r-coordinating earth attached to the nitrogen atom is tT), the abbreviation ford refers to the foramidinate (regardless of the R-coordination group attached to the nitrogen atom); the abbreviation "guam" refers to the sulfhydryl group. (guamidinate) (regardless of the R ligand attached to the nitrogen atom); the abbreviation dab is a block of butadiene (regardless of the r-coordination attached to the nitrogen atom); and the fine-grained PCAI system, refers to; The imine group D is called (regardless of the R ligand attached to the nitrogen atom). For a better understanding, the general structure of these ligands is represented as follows, wherein each R is independently selected from the group consisting of Η.γ Γ1 ancient a* .. _ into the H, Ci_C6 linear, branched, or cyclic alkyl or An aryl group; an amine substituent such as NRiR2 or NR1R2R3, wherein Ri, r2 and R3 are independently selected from fluorene or Cl_C6 straight-chain, branched, or cyclic alkyl or aryl; and the oxygen-burning substituent is such as (10) or qr1r2 Wherein r2 is independently selected from the group consisting of hydrazine and a Ci-C6 linear, branched, or cyclic alkyl or aryl group. 201120232 HIC( RIC(

R

N

N base month armor

R

N I R

N

R

R —Ν Ν — R Dibutadiene base Month C*

R - C /

R

ο ο 乙乙丙基

Diketimine 0 N —R enaminone burst

Μ, R2,. i V R5 m-nr'r2r3 m-or4r5 SUMMARY OF THE INVENTION The disclosed method is a method of depositing an alkaline earth metal fluoride film onto one or more bases. A reactor containing at least one substrate disposed therein is provided. The vapor of the earth metal precursor is introduced into the reactor. The alkali drive has the formula: MXl〇x-nX20x-mLp (I) wherein: two are a town, a ruthenium, a ruthenium or a ruthenium, preferably a magnesium; an alkenyl group, and the ring 1 is selected from the group consisting of cyclopentadienyl and ruthenium. The dilute group, the cyclohexanediyl group, the hexamethylene group, the heptadienyl group, the dienyl group and the octadienyl group are preferably a cyclopentadienyl group; the 'x system is selected from the group consisting of 7 A group consisting of acetylacetonate and dilute amine g with its 201120232 (enaminoketonate), diketimine, dioxadiene, amidinate, sulfhydryl and thiol (gnate) -L is a Lewis test; • ox is an integer representing the oxidation state of the molecule; • -n is an integer selected from 〇 and οχ, preferably 〇 or 2; -m is selected from 〇 and ox An integer, preferably 〇 or 2; - η and m are selected such that the sum of η and m is equal to ox; and -P is an integer between 0 and 2, preferably 1. In the vapor deposition method, 'vapor and The substrate is contacted to form a soil-measuring metal film selected from the group consisting of MgF2, CaFz, SrF2, and BaF2 on at least one surface of the substrate. The disclosure method may include one or more of the following: • alkaline earth Metal precursor is chosen from the group consisting of; MgCp2,

Mg(MeCp)2, Mg(EtCp)2, Mg(PrCp)2, Mg(BuCp)2, Mg(acac)2, Mg(tmhd)2, Mg(od)2, Mg(tfac)2, Mg( Hfac)2

Mg(hfac)2 tetraethyl oxime: fij|, Mg(nihd)2, Mg(dibni)2

Mg(tmod)2, Mg(ibmp)2, Mg(Et-dkti)2, Mg(Et-emk)2, Mg(iPr-amd)2, Mg(iPr-form)2,

Mg(N,N'-Et2-N''-Me2-guam)2, Mg(N,N'-tBu2-dab)2 and combinations thereof are preferably Mg(MeCp)2, Mg(EtCp)2 Mg(Et-dkti)2 and Mg(tmhd)2; • Vapor includes a solvent for dissolving the alkaline earth metal precursor; • The reactor has a range from about 25 ° C to about 300 ° C, preferably about 5 (TC to About 250 ° C 'and more preferably about 1 〇〇. 〇 to about 20 (TC temperature; 201120232 • The reactor has between about 0.0001 Torr (〇〇 13333 Pa) to about 1 Torr (133, 322 Pa), Preferably, the pressure is between about 1 3 33 Pa to about 3 Torr (39,997 Pa); • The vapor deposition method is selected from the group consisting of chemical vapor deposition (CVD) and atomic layer deposition (ALD). a plasma-reinforced CVD method and a plasma-enhanced ALD method; • introducing a co-reactant into the reactor to adjust the alkaline earth metal film; • reducing the refractive index of the soil-treated metal film by post-treatment; The vapor of the reactant is introduced into the reactor; • the vapor of the co-reactant is reacted with the vapor of the alkaline earth metal precursor before or at the same time as the contacting step; • the co-reactant is fluorine-containing but does not contain a metal source; The system is selected from the group consisting of NF3, hydrofluoric acid (HF), fluorine (F2), trifluorocarbon (CIF3), bromine trifluoride (BrF3), iodine trifluoride (IF3) and iodine pentafluoride (iFs). a group of people; and

• The co-reactant comprises oxygen, nitrogen and/or aluminum J. Also disclosed is a substrate coated with an alkaline earth metal film comprising the product of any of the methods described above. [Embodiment] The disclosed method is to enhance C VD, ALD and pulse CVD by heat and/or plasma in a range from about 25 t: to about 3 〇 (rc, preferably about 5 (rc to about 25 〇 < t a method of depositing a hafnium metal fluoride film at a temperature of from about 10 C to about 20 〇c. The disclosed method utilizes an alkaline earth metal precursor and a fluorine co-reactant

S 8 201120232 combination. The fluoroco-reactant is non-solid at room temperature and does not contain any other metal atom β ϋ or gas. The disclosed soil precursor has a lower jaw. MX ox-nX2〇x.mLp - Μ is magnesium, calcium , hydrazine or hydrazine, preferably magnesium; cyclohexadienyl, hexadienyl and octadienyl, enaminone group; -X is selected from cyclopentadienyl, pentadienyl diene a group consisting of a base, a cycloheptadienyl group, a heptadienyl group, and a cyclooctyl group, preferably a cyclopentadienyl group; the -X group is selected from the group consisting of an enaminoketonate and a diketimine group. -L is a Lewis test; -ox is an integer representing the oxidation state of the molecule; -η is an integer selected from 〇 and ox, preferably 〇 or 2; -Hi is an integer selected from 〇 and ox Preferably, 〇 or 2; -η and m are selected such that the sum of n + m = 〇χ ; and -Ρ is an integer between 0 and 2, preferably 1. Each of XI and Χ2 may each be substituted by: Ci C: 4 linear or branched alkyl, CyC: 4 cycloalkyl; q-C4 alkylamine straight or branched fluoroalkyl; or Cs-C4 cyclofluoride alkyl. The fluorinated alkyl group can be fluorinated in a range from partial fluorination to full fluorination in the group and F molecules (i.e., ruthenium free substituents) at each available position in the alkyl group. The Lewis base may be selected from the group consisting of tetraglyme 'triethylene glycol dimethyl ether, dimethyl ether, tetrahydrofuran, and pyridyl. Set or a combination thereof. 201120232 Exemplary soil precursors include MgCp2, Mg(MeCp)2, Mg(EtCp)2, Mg(PrCp)2, Mg(BuCp)2, Mg(acac)2, Mg(tmhd)2, Mg( Od) 2' Mg(tfac)2, Mg(hfac)2, Mg(hfac)2 tetradide dioxime ether, Mg(mhd)2, Mg(dibm)2, Mg(tmod)2, Mg(ibmp) 2 'Mg(Et-dkti)2, Mg(Et-emk)2, Mg(iPr-amd)2, Mg(iPr-form)2 'Mg(N,N'-Et2-N''-Me2-guam 2, Mg(N, N'-tBu2-dab) 2 and combinations thereof. Preferred alkaline earth metal precursors include Mg(MeCp)2, Mg(EtCp)2, Mg(Et-dkti)2 or Mg(tmhd)2. Many of these examples are commercially available. Those that are not commercially available can be synthesized by methods known in the art. The disclosed fluoroco-reactants are free of metallic elements which help to reduce the contamination of the soil ferrite film that is obtained. Exemplary fluoroco-reactants include nf3, hydrofluoric acid (HF), fluorine (f2), trifluorocarbon (c1F3), bromine trifluoride (BrF3), iodine trifluoride (IF3), and iodine pentafluoride. (IF5). Exemplary fluoro-co-reactants are commercially available as soil test metal precursors and fluoro-co-reactant systems for use in forming a soiled metal fluoride layer on a substrate by vapor deposition. ,. This method is useful in the manufacture of semiconductors, photovoltaics, LCD_TFT or planar components. The method comprises: providing a reactor having at least one substrate disposed therein; providing the alkaline earth metal precursor; vaporizing the alkaline earth metal precursor; introducing a vapor of the alkaline earth metal precursor into the reactor; and bringing the alkaline earth metal to the v portion The vapor of the precursor is deposited on the substrate to form a film comprising the soil precursor metal precursor. The square > alkaline earth metal precursor (hereinafter referred to as "precursor") can be deposited using any gas phase π Ή矹 phase Λ槚 method known to those skilled in the art to form an alkaline earth 201120232 metal-containing film. Examples of suitable deposition methods include, but are not limited to, conventional chemical vapor deposition (CVD), low pressure chemical vapor deposition (LpcvD), atomic layer deposition (ALD), pulsed chemical vapor deposition (p_CVD), plasma enhanced atomic layer deposition. (PE-ALD) or a combination thereof. The type of substrate on which the film will be deposited will vary depending on the intended end use. In some embodiments, the substrate may be selected from the group consisting of Metal Insulator Metal (MIM-structure for capacitors), Dynamic Random Access Memory (DRAM), and Ferroelectric Random Access Memory (FeRam) technology. Used as a dielectric material or as an oxide of a gate dielectric in a complementary metal oxide semiconductor (CM〇s) technology (for example, a material mainly composed of Hf〇2, a material mainly composed of Ti〇2, a material mainly composed of Zr〇2, a material mainly composed of a rare earth element oxide, a material mainly composed of a ternary oxide, or the like) or selected for use between copper and a low dielectric layer (l〇wk layer) A nitride-based film of an oxygen barrier (for example, TaN). Other substrates can be used in the fabrication of semiconductors, photovoltaics, lcd_tft or planar components. Examples of such substrates include, but are not limited to, solid substrates such as metal substrates (e.g., Au, pd, Rh, Ru, w, ab, Ti, C, Pt, and metallazine such as TiSi2, c〇si2). , Nisu N(8)2); metal-containing vaporized substrates (eg, TaN, TiN, WN, TaCN, TiC: N, TasmTlSiN); semiconductor materials (eg,

InP, diamond, GaN and SlC); insulator (eg si〇2, with claws, si〇N, Hf02, Ta2〇5, Zr〇2, Ti〇2, Al2〇3 and barium titanate); or other inclusions These (iv) any number of combinations of substrates. The actual substrate may also depend on the particular precursor used. However, in many instances, the preferred substrate for use will be selected from substrates based on Hf 〇 2, Tl 〇 j Zr 〇 2 . 11 201120232 The precursor is introduced into the reaction chamber containing at least one substrate in vapor form. The reaction; t can be any enclosure or chamber of the apparatus in which the deposition method is performed, such as, but not limited to, a parallel plate reactor, a cold wall reaction S 'hot wall reactor, a single wafer reaction , multi-chip reactors or other such types of deposition systems. The reaction chamber can be maintained in the range of about 托1 Torr (〇〇13 pa) to about ι〇〇〇托 (13.33\104?&), preferably about 〇1 Torr (13 33 1^) to about 3 〇〇 (4〇X 10 Pa) under pressure. In addition, the reaction chamber temperature may range from about 25 to about 300. (:, preferably about 5. 〇〇 to about 2$ 〇 β (:, and more preferably about 1 ° C to about 200 ° C. The substrate can be heated to a sufficient temperature at a sufficient growth rate Obtaining the desired film with the desired physical state and composition. The non-limiting exemplary temperature range over which the substrate can be heated includes from about 25 scoops to about 3 Torr (Γ(:β substrate temperature is between about 100 ° C and about 200) °c is better. The precursor can also be sent to the gasifier in a liquid state, which is first vaporized in the gasifier before being introduced into the reaction chamber. The precursor can be optionally combined with - or a plurality of gases before it is vaporized. Mixing a solvent, one or more metal sources/and a mixture of one or more solvents and or a plurality of metal sources. The solvent may be selected from the group consisting of methyl bromide, ethylbenzene, xylene, mesitylene, decane, dodecane, octane. a group consisting of hexane, pentane or other solvent. The resulting concentration may range from about 〇 to about 2 M. The metal source may comprise any metal moon J filter currently known or later developed. Alternatively, the precursor may be Passing a carrier gas into the sump containing the precursor or by bubbling the carrier gas into Precursor vaporized. The carrier gas

S 12 201120232 The body and precursor are then introduced into the reaction chamber. If necessary, the vessel can be heated to a temperature that allows the precursor to be in its liquid phase and have a sufficient vapor pressure. The carrier gas can include, but is not limited to, Ar, He, N2, and mixtures thereof. The precursor can be mixed in a container with a solvent, other metal precursor or a mixture thereof as needed. The container can be maintained at a temperature range such as 〇 _ i 5 〇〇 c. Those skilled in the art understand that the temperature of the thief can be adjusted in a known manner to control the amount of precursor to gasification. The temperature and pressure in the reactor are maintained under conditions suitable for ALD or CVD deposition. In other words, the conditions within the previously disclosed chamber are such that at least a portion of the vapor introduced into the reaction chamber is deposited on the substrate to form a layer containing the soil. In addition to the selective mixing of the precursor with the solvent, the metal precursor, and the stabilizer prior to introduction into the reaction chamber, the precursor can be mixed with the co-reactant species in the reaction chamber. Fluoride co-reactants disclosed by the co-reactant species are preferred. Depending on the desired use of the film to be applied, the co-reactant may also include a pore forming agent such as bicycloheptadiene or other unsaturated carbocyclic molecules. The resulting film can be subsequently processed to form voids, such as uv hardened or heated, but preferably less than 25 (temperature above rc. The incorporation of voids in the alkaline earth metal fluoride film will reduce the refractive index of the film. Because oxygen permeation may damage microlenses in CIS, in these applications, porosity should be used arbitrarily. Other exemplary co-reactant species include, but are not limited to, Ha, metal precursors such as trimethylaluminum ( TMA) or other aluminum-containing precursors, other precursors containing strontium

Group B 13 201120232 (TaWC^hWNC^3) 3] or TBTDET), dimethylaminoethoxytetraethoxy oxide button (TAT-DMAE), pentaethoxy ruthenium (pET), tertiary butyl Imino ginseng (diethylamino) hydrazine (tBTDEN), pentaethoxy hydrazine (pEN), and combinations thereof 0 When the desired film also contains oxygen, for example, and not limited to, a town of dioxide, The co-reactant species may include an oxygen source selected from, but not limited to, 02, 〇3, H20, H2〇2, acetic acid, formalin, polyoxymethylene, and combinations thereof. Alternatively, the source of oxygen may be selected from the group consisting of 〇2, H2〇, 〇3, h2〇2, carboxylic acids or combinations thereof. When the desired film also contains nitrogen, such as, for example and without limitation, MgON, the co-reactant species may include a nitrogen source selected from, but not limited to, nitrogen (N2), ammonia, and alkyl derivatives thereof. Rhodium and its alkyl derivatives, nitrogen-containing free radicals (eg, N, NH, NH2), NO, N20, N02, amines, and any combination thereof. When the desired film also contains carbon, 'for example, and without limitation, magnesium carbide, the common reactant species may include carbon sources selected from, but not limited to, methane, ethane, propane, butane, ethylene, Propylene, tertiary butene, isobutylene, CC14, and any combination thereof. When the desired film also contains ruthenium, such as, for example and without limitation, MgSiOx, the co-reactant species may comprise a source selected from the group consisting of, but not limited to, SiH4, Si2H6, Si3H8, and diammonium. ) TriDMAS, bis(dimethylamino) zebra (BDMAS), bis(diethylamino) oxime (BDEAS), guanidine (diethylamino) oxime (TDEAS), ginseng Dimethylamino) strontium (TDMAS), hydrazine (ethyl decylamino) decane (TEMAS) '(SiH3)3N, (SiH3)2〇, three s 14 201120232 oxalate, dioxane , tridecylamine, dioxane, trioxane, alkoxy oxime SiHJOR1). , sterol SUOHWOR1) ^ (preferably SVOHKOR1: ^; more preferably Si(OH)(OtBu)3), amino decane (where X is ι, 2, 3 or 4:111 and R2 is independently Η or straight Chain, branched or cyclic Cl-C6 carbon chain; preferably TriDMAS, BTBAS and/or BDEAS) and any combination thereof. Alternatively, the target film may contain ruthenium (Ge), and in the above examples, the ruthenium-containing reactant species may be substituted for the ruthenium-containing reactant species. When the desired film also contains other metals, for example, and not limited to: Ti, Ta, Hf, Zr, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb Or a combination thereof's the co-reactant species may comprise a second precursor selected from the group consisting of, but not limited to, a metal alkyl group such as SbRi'3 or SnR1 4 (wherein each R1 is independently oxime or linear, branched or a cyclic C1-C6 carbon chain), a metal alkoxide such as St^OR1;^ or Si^OR, (wherein each R1 is independently a fluorene or a straight bond, a bond or a cyclic C1-C6 carbon bond), and a metal Amine such as si^ni^rWni^rInrSr6) or

Ge(NR1R2)(NR3R4)(NR5R6)(NR7R8) (wherein each of Ri, R2, R3, R4, R5, R6, R7 and R8 is independently H, C1-C6 carbon chain or trialkyl fluorenyl' And each of the three sulphur groups is linear, branched or cyclic) and any combination thereof. The precursor and one or more co-reactant species can be introduced simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or other combinations into the reaction chamber. For example, the precursor can be introduced by one pulse and two additional metal sources can be introduced together with individual pulses [improved atomic layer deposition]. Alternatively, the reaction chamber may already contain a co-reactant species prior to introduction of the precursor at 15 201120232. The co-reactant species can be broken down into free radicals by a plasma system located in the transport reaction. Alternatively, the precursor can be introduced continuously into the reaction chamber while other metal sources are introduced by pulse (pulsed chemical vapor deposition). In each case, the pulse may be followed by a rinse or vacuum step to remove excess introduced components. In each of the examples, the pulse may last for a period of from about 1 second to about 1 second or from about 33 seconds to about 3 seconds, or from about 0.5 seconds to about 2 seconds. In an ALD or pEALD process, an annealing or flash annealing step can be performed after each ALD cycle or preferably after a ALD cycle (e.g., every 2 to 丨〇 ALD cycles). The deposition cycle performed between each annealing step can be adjusted; the number of turns maximizes film properties and throughput. The substrate may be exposed to a temperature ranging from about 4 Torr to about 1000 C at a temperature ranging from about 4 Torr to about 1000 C for a period of about 〇1 sec to about 120 sec. The inch film can contain less impurities, so the film will have an improved density' resulting in improved leakage current. The annealing step can be performed in the same-reaction chamber in which the deposition method is performed. Alternatively, the substrate can be removed from the reaction chamber while the annealing/rapid annealing method is performed in a different device. In a non-limiting exemplary atomic layer deposition type process, the vapor phase of the alkaline earth metal precursor is introduced into the reaction chamber' which is in contact with a suitable substrate in the reaction chamber. Excess precursor can then be removed from the reaction chamber by flushing and/or vacuuming the reaction chamber. The fluoroco-reactant is introduced into the reaction chamber where the fluoroco-reactant is reacted in a self-limiting manner with the adsorbed precursor. Any excess fluorine co-reactant is removed from the reaction chamber by flushing and/or vacuuming the reaction chamber. If the desired film is a soil test metal

S 16 201120232 (d) The two-step process provides the desired film thickness or can be repeated until a film having the necessary thickness is obtained. Alternatively, if the desired film is an alkaline earth metal i film containing a second metal, the second two-step process can be followed by vapor conduction of the second precursor: a reaction chamber. The second precursor will be selected based on the deposition of the alkaline earth metal dry film deposited and may include a carbonaceous precursor. After the introduction of the reaction chamber, the first month of the horse area and the substrate are connected to each other. Any excess second precursor is removed from the reaction chamber by flushing and/or evacuating the reaction chamber. Again, the fluoroco-reactant can be introduced into the reaction chamber to react with the second precursor. Excess gas co-reactants are removed from the reaction chamber by flushing and/or evacuating the reaction chamber. This method is terminated if the desired film thickness has been reached. However, if a thicker film is required, the entire four-step method can be repeated. #Alternatively providing a precursor, a second precursor, and a fluorine co-reactant, a film of the desired composition and thickness can be deposited. The alkaline earth metal fluoride film obtained from the above discussion may include MgF2'CaF2'SrF2 and BaF2. One of ordinary skill will appreciate that the desired film composition can be obtained by clearly selecting the appropriate precursor and co-reactant species. EXAMPLES The following examples illustrate experiments performed in conjunction with the disclosure herein. The examples are not intended to be all inclusive, and are not intended to limit the scope of the invention disclosed herein. The liquid of the predictive example 1.1 was deposited using a MgF2 film of Mg(EtCp) 2 and F2. Mg(EtCp)2 is a relatively high vapor pressure of 0.18 Torr at 52t. The vapor of Mg(EtCp) 2 can be mixed with the f2-containing mixture in the reactor. The F2-containing mixture can be 1% F2 in nitrogen. The reaction can be carried out at temperatures below 200 ° C and forms a high purity MgF 2 film (no carbon, but also no oxygen, as it does not appear in this method.) It should be understood that those skilled in the art can already The details, materials, steps, and arrangement of the details of the present invention are set forth in the description of the invention. Therefore, the present invention is not intended to be limited to the embodiments set forth above and/or the specific embodiments of the accompanying drawings. [Simple diagram description] None [Main component symbol description] None;

Claims (1)

201120232 VII. Scope of Application: 1. A method of depositing a soiled metal fluoride film onto one or more substrates, comprising: a) providing a reaction benefit and at least one substrate placed in the reactor; b) having The alkaline earth metal precursor vapor of the following formula is introduced into the reactor MX ox-nX2〇x.mLp (I) wherein: - lanthanum is magnesium, calcium, strontium or barium, preferably magnesium; -X1 is selected from cyclopentane a group consisting of an alkenyl group, a pentadienyl group, a cyclohexanediyl group, a hexadienyl group, an azepinedienyl group, a heptadienyl group, a cyclooctadienyl group, and an octadienyl group, preferably a cyclopentane group Alkenyl; lanthanide selected from the group consisting of acetylacetacetate, aminoketonate, diketiminate, amidlenate, amiddinate And a group consisting of guamidinate; • L· is a Lewis base; • ox is an integer representing the oxidation state of the molecule; η is selected from an integer of 0 and preferably '0 or 2; The signal is selected from an integer between 〇 and ox, preferably 〇 or 2; and the melon is selected such that the sum of η and m is equal to 〇 x ; and _P is between. And an integer of 2, preferably in the gas phase, in which the vapor is brought into contact with the substrate on a surface of the substrate to form a group selected from the group consisting of MgF2, CaF2, SrF2, and BaF2. Earth metal film. 19 201120232 2 The method of claim 1, wherein the soil precursor metal precursor is selected from the group consisting of MgCp2, Mg(MeCp)2, Mg(EtCp)2, Mg(PrCp)2, Mg (BuCp) 2, Mg (acac) 2, Mg (tmhd) 2, Mg (od) 2, Mg (tfac) 2, Mg (hfac) 2, Mg (hfac) 2 tetraethylene glycol dimethyl ether, Mg ( Mhd)2 Mg(dibm)2, Mg(tmod)2, Mg(ibmp)2, Mg(Et-dkti)2, Mg(Et-emk)2, Mg(iPr-amd)2, Mg(iPr-form 2, Mg(N,N'-Et2-N''-Me2-guam)2, Mg(N,N,-tBu2-dab)2 and combinations thereof are preferably Mg(MeCp)2, Mg(EtCp 2, Mg(Et-dkti)2 and Mg(tmhd)2. 3. The method of claim i or item 2, wherein the vapor comprises a solvent for dissolving the alkaline earth metal precursor. 4. The method of any one of clauses 1 to 3 wherein the reactor has a range from about 25 ° C to about 300 ° C, preferably from about 50 ° C to about 250 ° C, and Better about 1 inch. 〇 to about 2 〇〇. 5. The method of any one of claims 1 to 4 wherein the reactor has a range of from about 0.0001 Torr (〇〇1 3333 pa) to about 1 Torr ( 133,322 Pa) 'preferably between about ο 」 (丨3 33 pa) to about 300 (39,997 Pa). 6_, as in the method of any one of claims 1 to 5, The vapor deposition method is selected from the group consisting of chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced CVD, and plasma enhanced ALD. The method of any one of item 6, further comprising introducing a co-reactant into the reactor to adjust the alkaline earth metal thin 20 201120232 Membrane. 8. The method of any one of clauses i to 7 of the patent application, further comprising reducing the refractive index of the alkaline earth metal thin crucible by a post-treatment method. The method of any one of clauses 1 to 8, further comprising: a) introducing a vapor of the co-reactant into the reactor; and b) bringing the co-reactant before or simultaneously with the contacting step The vapor reacts with the vapor of the alkaline earth metal precursor. 10. The method of claim 9, wherein the co-reactant contains fluorine but does not contain a source of metal. 11. The method of claim 1, wherein the co-reactant is selected from the group consisting of NF3, fluorofluoric acid (HF), fluorine (6), three gasification gas (C1F3), three gas evolution (BrF3), three A group consisting of cesium fluoride (IF3) and a pentafluoride dish (A). △ The method of claim 7, wherein the co-reactant comprises oxygen, nitrogen and/or aluminum. A substrate coated with an alkaline earth metal-containing film, which comprises the product of the method of any one of items 1 to 12 of the patent application. Eight, schema: (none) 21