TW575679B - Low temperature CVD processes for preparing ferroelectric films using Bi aryls - Google Patents

Description

Printed by the Employees ’Cooperative of the Bureau of Wisdom and Finance of the Ministry of Economic Affairs, 575679 A7 B7 V. Description of the Invention (ί) Background of the Invention: This invention is to provide a metal oxide film containing B i by chemical vapor deposition method. The surface of the substrate is formed by decomposing a precursor of Bi oxide. In recent years, there has been increasing interest in ferroelectric materials due to its use in non-volatile memory. The capacitor plate formed by a thin ferroelectric film is polarized and can be used for information storage. This capacitor is connected to a transistor, and the two form a storage cell. This storage cell controls the mechanism for the electrons to read the signal in the capacitor. The information stored in the unit cell can be applied to the thin ferroelectric film by an electric field, and the polarization effect can be changed. Ferroelectric Random Access Memory (FERAMs), unlike DRAM (Dynamic Random Access Memory), will retain the stored information when the power is turned off. In addition, it does not need to be repeated. Sexual re-injection information, the electrical characteristics required for ferroelectric materials to be used in memory include: (a) a mandatory electric field can be used at low voltages; (b) a highly reducing polarization Characteristics, can be reliable for the storage of information; (c) minimal fatigue, which is a requirement on a long life cycle; and (d) no imprint characteristics, because imprints will change the stored information.缌 _Bismuth Giant Hydrochloride (SrBi2Ta 20 9) (SBT) is a ferroelectric material that meets all the above requirements. The most important thing is that it can be made and integrated into memory elements. The capacitance of CBT is The gel method is used to make good electrical components. This Sol-gel method only provides SBT with low density. In order to achieve high-density integrated SBT, a different method: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — »-------------- ----- Order --------- line (please read the precautions on the back before filling this page) 575679 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Invention Description (>) CVD will be used. SUMMARY OF THE INVENTION In one aspect, the invention is characterized by the use of Bi oxides and decomposition reactions on a substrate at temperatures below 450 ° C to form Bi-containing metal oxides. This Bi complex contains at least one aromatic group and is used as a precursor of Bi oxide. This invention illustrates this simplified view, which includes one or more of the following features. The B i oxide precursor can be dissolved in a solution before being decomposed, and the deposition temperature can be less than 400 ° C. The B i oxide can also be provided by the decomposition of an S r oxide, and the same Ground, oxides of sr and Ta can be formed from Ta oxide precursors, and oxides of Bi, Sr, and Ta can be deposited on the base material.

The oxide films of Bi, Sr, and Ta can be deposited as a ferroelectric film, or converted into a ferroelectric film by an annealing process. This Bi-containing metal oxide film can be formed on the substrate by CVD. The deposition temperature of the substrate is lower than 450 ° C. It contains gases of the precursors of Bi, Sr and Ta oxides in CVD. For this precursor Decompose thermally and deposit this oxide on the substrate. Bi, Sr, and Ta oxide precursors can be decomposed by the decomposition of the oxide in the presence of the oxidant. Here, the oxidant sample contains 〇2 , Single 〇2, 〇3; Η202, Ν20; ΝΟχ (1 ^ χ $ 3), and gas flow type 0 2 plasma, and the solubility of the oxidant here is 5% and 95% of the total gas amount in CV. In D, at least one kind of O 2 and N 20 can be used as an oxidant, and the oxidant can be plasma-plasmidized by CVD, UV light, and Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ---------—----- Order ------.— line-4 ^ " (Please read the notes on the back before filling out this page) 575679 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7___ printed by the consumer cooperative V. Description of the invention (4) The thermal sensor or ion beam converts the oxidant molecule to an activated oxidant. The precursor of this Bi oxide can be the formula Bi (ph) 3 or Bi (ph (R)) 3, where R is fluorine, aromatic, alkyl or amine. Examples of several Bi oxide precursors Bi (phenyl (R)) 3, where R is 2 ~ 4, which can be methyl, ethyl, propyl, butyl or pentyl; Bi (phenyl (R ') 2 ) 3, where the R 'group has two positions, from 2 to 5, can be Et, Pr,' Pr or, Bu; Bi (phenyl (R '') 3) 3, where R "is Me, Et, Pr , 'Pr or fBr; Bi (tetraalkylphenyl) 3; Bi (pentaalkylphenyl) 3; B i (a 1 coxypheny 1) 3, where the alcoxy group can be from 2 to 4, and the alcoxy group in the aromatic component is i4e, Et, Pr, JPr ^ fBu; Bi (dialcoxypheny) 3, S φ alcoxy group may be a selected position from 2 to 5, and the alcoxy of the alkyl component is Me, Et, Pr, 'Pr or' Bu; Bi ( dialkylamino-phenyl) 3, where the amine group can be selected from 2 to 4, where the alkyl group is Me, Et, Pr, fPr or 4 \ 1; Bi (bis- (dialkylamino) -phenyl) 3, where the amine group is Select from 2 ~ 5 positions, and the alkyl group is Me, Et, Pr, fPr or ju; Bi (flu〇r〇Phenyl) 3, where the fluorine atom is selected from 2 to 4 positions; Bi (difluoro-phenyl) 3, where the fluorine atom is selected from 2 to 5, Bi (trifluoro-pheny l (R)) 3, where the fluorine atom is the 3 position selected by 2 ~ 5; Bi (tetrafluoro-phenyl) 3, where the fluorine atom is selected from the position of 2 ~ 5; Bi (pentafluoro-phenyl) 3. This Bi The oxide precursor also contains Bi (o-tolyl) 3, Bi (m-tolyl) 3, Bi (p-tolyl) 3, Bi (2,4-dimethylphenyl) 3, and Bi (2,4,6-trimethylphenyl) ) 3, Bi (4-tert-butyphenyl) 3, Bi (2,4,6-trialkylphenyl) 3, Bi (4-methoxyphenyl) 3, Bi (4- (N, N-dimenthy) -phenyl) 3, Ben Paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) ---------------------- Order --------- line (Please read the precautions on the back before filling out this page) 575679 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of Invention (4) and Bi (4-fluorophenyl) 3. The Bi-containing metal oxide is deposited on the substrate and can be represented by the formula (BLOJ'AwB w03w + 1) 2-, where A is Bi3 +, L3 +, L2 +, Ca2 +, Sr 2+, Ba 2+, Pb 2+, or Na +, B is F e 3+, A1 3+, S c 3+, Y 3+, L 3+, L4 +, Ti4 +, Nb5 +, Ta5 +, W6 + or Mo6 +, and L is Ce4 +, La3 +, Pr 3+, Ho 3 +, Eu 2+ or Yb 2+, of which 1 S m S 5. This Bi-containing metal oxide can also have the formula Bi2W06; BiM03, where M is Fe or Mn; Ba2BiM06, where M is V, Nb, or Ta; Pb2BiM06, where M is V, Nb, or Ta; Ba3Bi2M09, where M is Mo or W; Pb6BiM018, where M is Mo or \ ¥; ^^ 11 ^ 20 6 or K2BiNb5015. These metal oxides can be obtained by the decomposition of the aforementioned metals containing precursors. The Bi-containing metal oxides can also be formulated as Bi 4Ti 30 12; PrBi 3Ti 30 12; HoBi 3Ti 3〇12; LaBi3Ti3〇12; Bi 3TiTaO 9 ; Bi3TiNb〇9;

SrBi 4Ti 40 15; CaBi 4Ti 4 〇 15; BaBi 4Ti 40 15; PbBi 4Ti 4 0 15; Sr 2Bi 4Ti 50 18; Ca 2Bi 4Ti 50 18; B a 2 B i 4 T i 50 18;

Pb 2Bi 4Ti 50 18; SrBi 5Ti 4FeO 18; CaBi 5Ti 4FeO 18;

BaBi 5Ti 4FeO 18; PbBi 5Ti 4FeO 18; Bi 5Ti 3FeO 15;

LaBi 4Ti 3FeO 15; PrBi 4Ti 3FeO 15; Bi 6Ti 3FeO 18; 3191 ^ / 65〇27; 31 * 1 _; ^ _ 2 € 3; ^ & 1 ^ 1326141 ^ 4〇15, of which 0 $ and S1, 〇SY $ l, and 0 $ ZSl; Sr 2_ [F_zCa Ja yPb zBi 4Ti 50 18, of which 0SXS2, 0SYS2, and Q, SZ $ 2; or SruuCazBayPbzBiJi ^ FeOe, of which 0SXS1, OSYS 1, and 0SZS1, a metal oxide element, may be Replaced by Ce, La, Pr, Ho, Eu and Yb. This paper size applies to China National Standard (CNS) A4 specification (210 χ 297 mm) ---------------------- Order --------- Line ( Please read the notes on the back before filling out this page) 5. _I __—————————— Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 Instructions (π) This Bi-containing metal oxide film may SBT is a derivative of SBT. Examples of several derivatives include SrBi2Ta2O9; SrBi2Ta2_xNbz09, where 0 $ χ $ 2; SrBi2Nb209; Sr ^ Ba ^ BisTa 2_yNb y09, where 0SXSl, and 0SYS2; SruCazBi2Ta 2_yNb y09, where OSX ^ l, and 0S YS 2; SruPb ^ BiJayNbyC ^, among which OSXS1 and OSY S 2, or S r u_y_z Ba especially Ca yPb zBi 2Ta 2 -p > N bp09, among which osxg 1, OSYS, OSZS1, and OSP2. An oxide of a metal element may be replaced by a metal such as Ce, La, Pr, Ho, Eu, and Yb. This Sr oxide precursor usually has the formula Sr (thd) 2 or Sr (thd) 2 additives, and can contain polyester or polyamine compounds. This polyester has the formula such as RC ^ CH'Heh-R ', where 2SnS6 , And where R and R 'can be independently alkyl, aromatic, or hydrogen, this polyamine has the formula R-NRH ^ CH'HzNRnh-R', where 2SnS6, where R and R 'can be independently alkane Group, aryl group or hydrogen, and R "is hydrogen, Me, Et or Pr. This Sr oxide precursor also contains tetraglyme, triglyme, and N, N, N ', N' ', N"-pentamethyl-diethylene -triamine or N, N, N ', N ", NM', NM, -hexamethyl-triethylene-tetramineo

The precursor of Ta oxide usually has the formula of Ta (OR) 5_n (X) w, where R is Me, Et, Pr, 'Pr, Bu,) Bu,' Bu, pentyl, where X is a-diketonate and 1 ^ η ^ 5, for example, this precursor may be Ta (0 / prKthd). The Bi, Sr, and Ta oxide precursors are all soluble in an aliphatic compound, a cycloaliphatic compound, or an aromatic solvent, and may contain a functional group such as an alcohol, an ester, a fe, an amine, a ketone, and an aldehyde group. For example, Bi, Sr, Ta oxygen-7- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------------- --Order --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (^) Soluble recipes such as octane, nonane, decane, undecane, dodecane, tridecane, or tetradecane 'samples' These precursors are soluble in some mixtures such as: THF, tetraglyme with' PrOH ratio 8: 2: 1, and likewise, THF, fPrOH, and polyamine each have a ratio of about 8: 2: 1, and octane, decane, and pentametlyl-diethylane-triamine in a ratio of 5: 4: 1. Solutions containing these precursors can be gasified, for example, Bi oxides containing these precursors can be gasified at a temperature of 170 ° C ~ 250 ° C. An Ar, He or N 2 or gas is injected into the In the solution vapor, the vapor forming the input gas and the precursors of Bi, Sr, and Ta oxides is mixed at a ratio of 2: 1: 2. The most suitable concentration in this vapor mixture is related to several factors, which include the vapor Temperature, pressure in the evaporator, gas and vapor flow rates, the required stoichiometric ratio, and the geometry of the CVD internal chamber. In the CV D chamber, the substrate is heated to a temperature of 350 ° C to 45 ° C (the deposition temperature of the CVD chamber, and the pressure in the CVD chamber is maintained between 0.001 to 760 Torr, for example, 0.1 Torr to 100 Torr), and an additional gas is injected. In this CVD chamber, the concentration of the injected gas can be changed from 10% to 90% in the entire gas, and the vapor flows into the CVD chamber. For example, at a concentration of 30% to 50%, the appropriate precursor vapor, oxidant and injection gas It is introduced into the CVD chamber and injected at a standard flow rate of 1 ml / min ~ 15000 ml / min. The desired flow rate can also be the temperature and pressure of the mixture with gas and vapor. The required film chemistry The measurement and the geometry of the CVD chamber are related. These oxides are deposited on the substrate for more than 2 minutes to 2 hours, such as between 2 and 15 minutes. -8- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) --------------------- Order --------- line (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (7) After deposition, the film is heated to a temperature of 60 ° C ~ 80 ° 0 ° C for 5 minutes to 3 hours. This substrate preferably contains Si, n-doped Si, p-doped Si, Si02, Si3N4, GaAs, MgO, A1 20 3, Zr02, SrTi03, BaTi03 or PbTiO 3, this Bi-containing metal oxide film is deposited on a substrate containing an transistor, and is deposited on a bottom electrode, the bottom electrode is connected to the transistor through a plug, and the bottom electrode may include a kind of Metal, such as Pt, Pd, Au, Ir or Rh; a conductive metal oxide film, such as IrOz, RhOx, RuO /, OsOx, IU〇x or WO, where OSXS2;-a conductive metal nitride For example, TiNx, WNyTaNy, where 0SXS1, and 0 $ 1.7; or a superconducting oxide, such as YBa2Cu 30 7_y, where 0 $ XS 1, and Bi 2Sr 2Ca 2Cu 30 1Q, the bottom electrode may be a Pt electrode. The first interlayer may be provided between the bottom electrode and the plug. For example, the first interlayer includes an adhesion layer of Ti and a diffusion barrier layer of Ti nitride. The second interlayer may also be provided between the bottom electrode and the plug. Between the metal oxide layers, for example, the second dielectric layer includes a seed layer, a conductive layer, and a dielectric layer with a high dielectric constant. The plug includes W or Si, and the source and drain connected to the bottom electrode and the MOS field effect transistor. This film can also be used as a ferroelectric capacitor, a ferroelectric memory, and a ferroelectric thin film of a ferroelectric field effect transistor, For example, a metal ferroelectric semiconductor or a metal ferroelectric insulated semiconductor. The substrate can be exposed to the precursor vapor of the metal oxide before or after the gas and oxidant mixture is injected. The process of heating, decomposing and accumulating on the substrate must be at least two times. The substrate can also be removed from the chamber. At least one intermediate process, such as rapid thermal annealing, and then set to -9- Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------------- Order --------- line (please first Read the notes on the back and fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 ___________ B7 V. Description of the invention (4) Return to the room. The operation of CVD can also be changed. For example, the composition of the precursor, the oxidant, and the gas injected in the mixture can be changed while the substrate is in the CVD chamber. The Bi oxide precursor can be introduced into the CVD chamber from the start of deposition to 30 minutes later; the concentration of Bi oxide is gradually reduced. Another method is to heat the substrate at least twice at 450 ° C, or at least 2 and 03 oxidants are heated at 450 ° C in the room. According to another idea, the invention is characterized in that a metal oxide film is formed on the substrate, and the substrate is heated by not more than 45 0 ° C and introduction of Bi oxide precursor vapor onto the substrate. The complex of Bi contains at least one kind. The aromatic group is used as the precursor of Bi oxide. The Bi oxide precursor is decomposed on the surface of the substrate to form Bi oxide, and is deposited on the surface of the substrate. As used herein, the term "Bi oxide precursor" means any Bi complex that can be decomposed into Bi oxides, which contains Bi aromatic groups, which means that its structure is 3 or Bi (Ph (R) ) 3, wherein R is fluorine, aryl, alcohol or amine 'Bi aryl includes derivatives such as the precursors described above. The use of Bi aromatic groups as precursors of Bi oxides in CVD can provide some benefits. The B i aromatic group contains a B i-C bond, which is relatively easy to dissociate. Then, the B i aromatic group can be relatively low temperature. Decomposition by thermal decomposition at low temperature and deposition can reduce the migration of Bi oxides to the bottom electrode and the substrate. Such previously existing structures will be reduced. Unless there are other definitions, 'all the technologies here' have scientific terms that are common with one of the usual techniques. In this invention -1 0-This paper applies Chinese National Standard (CNS) A4 Specifications (210 x 297 male f) -------- Order ---------- ^ (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs System 575679 A7 B7 5. The technical description of the invention (?) Has the same meaning. Although these inserts can be used in the practice or testing of the invention, there are similar, similar or equivalent methods and materials. The methods and materials that are applicable are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. If there is a conflict, the current specifications, including definitions, etc. will be controlled. In addition, the materials , Methods, and examples are examples only and are not restricted. The features and benefits of other inventions will be described in detail below, as well as appearing in the scope of self-patenting. Brief Description of the Drawings Figure 1 is a simplified storage cell diagram of a ferroelectric memory. Figure 2 is a schematic diagram of an SBT layer inserted into a stacked capacitor with a transistor. Detailed description CVD can be used to provide Bi, Sr, and Ta oxide films on the surface of a substrate. This substrate can be used to make elements like storage cells. Referring to Fig. 1, a storage cell is formed by a layer of ferroelectric material 1 between a plate capacitor 2 and the capacitor 2 is connected to a transistor 3. The transistor has a single bit 4 and a signal line 5, which controls With the reading of the electrons in the capacitor 2, the ferroelectric layer 1 is able to store information by being polarized in a non-volatile manner. Referring to FIG. 2, a ferroelectric SBT layer 9 is inserted into a stacked capacitor with a transistor to form a storage cell. The stacked capacitor is located at the top of the transistor, and the bottom electrode 6 of the capacitor is connected by Formed by polycrystalline Si or W-11- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---- I --------------- Order --------- line (please read the precautions on the back before filling this page) 575679 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_______ V. Plug of the invention (P) 8 and In this MOSFET (metal oxide half field effect transistor), a ferroelectric layer 9 is disposed between the bottom electrode 6 and the upper electrode 10. CVD is used to provide the ferroelectric layers in Figures 1 and 2. For example, CVD is used to deposit metal oxides Bi, Sr, and Ta on a Pt / Ti / SiO 2 substrate. During CVD, the substrate is placed in a CVD chamber under low pressure and heated to the deposition temperature. The precursor is evaporated and then introduced into the CVD chamber. The precursor vapor is decomposed on the substrate surface and the metal oxide The molecules are deposited on the substrate to form a thin film. The CVD process has higher uniformity and better coverage than the metal oxide film formed by other processes. Further benefits of the CVD process include high uniformity, high density ’ability to produce very thin films, high yields and low manufacturing costs. For the Bi oxide Bi precursor, the Bi aromatic group, contains a Bi-C bond, which is relatively easy to dissociate, leading to the deposition of Bi oxides at low temperatures, for example, at 300 ° C. .

The oxides of Bi, Sr, and Ta can be deposited into a desired stoichiometric film, such as Bi 20 3-Sr0-Ta 20 5. This SBT film can be obtained by using Bi aromatic group as precursor of Bi oxide, and has high composition uniformity in water, high uniformity in surface structure, and high reproducibility. Bi, Sr, and Ta oxide films are formed by low-temperature deposition to form general non-ferroelectric materials, but ferroelectric properties can be obtained by conversion. After treatment, such as annealing, they can be converted into ferroelectric Aurivilius phases.

Bi aromatic group is used as the precursor of Bi gas. Generally, it has the structure of Bi (ph) 3 or Bi (Ph (R)) 3, where R is fluorine, aromatic group, alcohol group or an amine group. Several Bi aromatic groups Examples include: Bi (pheny 1 (R)) 3, where R is -12- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ϋ n ϋ I n ϋ ϋ u ϋ 1 nn ϋ -1 n ϋ IT --------- line (please read the notes on the back before filling this page) 575679 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of Invention (^) The position is selected from 2 to 4, and R is methyl, ethyl, propyl, isopropyl or spacer butyl; Bi (phenyl (R ') 2) 3, where R' group has two positions From 2 to 5, and R 'is Me, Et, Pr, 卞 1 or 411; Bi (phenyl (R ") 3) 3, where the R" group is selected from three positions from 2 to 5, and R " is Me, Et, Pr, 'Pr or' Br; Bi (tetraalkylphenyl) 3; Bi (pentaalkylphenyl) 3; Bi (alcoxyphenyl) 3, where the alcohol group is selected from 2 to 4, and where the aromatic group is 1 ^, £? 1: > 1: Or An; Bi (bis (dialkylamino) -phenyl) 3, in which the amine group is two selected positions from 2 to 5, where the aromatic group is Me, Et, Pr, 'Pr or' Bu; Bi (fluorophenyl) 3, where the fluorine atom is a selected position from 2 to 4; Bi (difluoro-phenyl) 3, where the fluorine atom is two selected positions from 2 to 5, Bi (trifluoro-phenyl) 3, where oxygen The atoms are three selected positions from 2 to 5; Bi (tetrafluoro-phenyl) 3, where the fluorine atom is from 2 to 5 and Bi (pentafluoro-phenyl) 3. This Bi oxide precursor also contains Bi (o-tolyl) 3, Bi (m-tolyl) 3, Bi (p-tolyl) 3, Bi (2,4-dimethylphenyl) 3, and Bi (2,4,6 -trimethylphenyl) 3, Bi (4-tert_butyphenyl) 3, Bi (2,4,6-trialkylphenyl) 3, Bi (4-methoxyphenyl) 3, Bi (4- (N, N-dimenthy) -phenyl) 3, and Bi (4-fluorophenyl) 3o All of these molecules can be oxidatively decomposed at very low temperatures. Then, these molecules can obtain Bi oxides under control and reproducibility. The preparation of other precursors can be found or referenced below. APPisarevskii et Inorg, chem, 35 (6), P.84 (1990); WA Hermann: ^, Chem Ber, 126, P.1127 (1993); RGGoel et al. J. Organomet. -13- This paper standard is applicable China National Standard (CNS) A4 specification (210 X 297 mm) ——--- * --------------- Order --------- line (please (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Invention Description (A)

Chem, 36, P.323 (1972); Bi-containing metal oxides deposited on substrates usually have the following structure: (Bi 20 3m + 1) 2- where A is Bi 3+, L 3+, L 2+, Ca 2+, Sr 2+, Ba 2+, Pb 2+ or Na +, and B is Fe 3+, Al 3+, Sc 3+, Y 3+, L 3+, L 4 +, Ti 4+, Nb 5+, Ta 5+, W 6+ or Mo 6+, where L represents a metal from the lanthanum series, such as Ce 4+,

La 3+, Pr 3+, Ho 3+, Eu 2+ or Yb2 +, and m is 1, 2, 3, 4 or 5, and several Bi oxides include:

Bi 2W0 6;

BiM03, where M is Fe or Mη;

Ba2BiM06, where M is V, Nb or Ta;

Pb2BiM06, where M is V, Nb or Ta;

Ba3Bi2M09, which is Mo or W;

Pb3Bi2M09, where M is Mo or W;

Ba6BiM018, where M is Mo or W;

Pb6BiM018, where M is Mo or W; KBiTi 20 6; and K 2BiNb 50 15 Bi-containing metal oxide may also have the following structure: Bi 4Ti 3012;

PrBi 3Ti 30 12; HoBi 3Ti 30 12; LaBi 3Ti 30 12; Bi 3TiTaO 9;

Bi 3TiNbO 9; SrBi 4Ti 40 15; CaBi4Ti4015; BaBi4Ti4015; PbBi4Ti4015; Sr 2Bi4Ti5018; C a 2 B i 4 Ti 50 18; B a 2 B i 4 Ti 50 18; Pb 2Bi 4Ti 50 18; SrBi 5Ti 4FeO 18; CaBi 5Ti 4FeO 18;

BaBi 5Ti 4FeO 18; PbBi 5Ti 4FeO 18; Bi 5Ti 3FeO 15; -1 4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 丨 丨 --------- --------- Order --------- line (please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 _ B7 V. Invention Instructions (4)

LaBi4Ti3Fe015; PrBi 4Ti 3FeO 15; Bi6Ti3Fe018;

Bl9Tl3Fe5〇27 'srny_2CaYBayPbzBi4Ti4015, where 0 $ X si, 〇 ^ Ym 〇sZ $ 1; Sr 2nzCayBayPbzBi4Ti5〇i8, where 0SXg2, 〇SY ^ 2, and 0SZS2; or. , 1, and OS 1, a metal oxide element can be used ,! ^,? ! *, Η〇, Eu and Yb. These B i -containing metal oxides have the advantage of non-ferroelectric properties, but can be transformed into ferroelectric oxides with layered superconductors such as the same Aurivilius phase through annealing. In addition, the preparation of these metal oxides can also be performed in The following references are found in the test: T. Kodas and MJ Hampden-Smith, The Chemistry of Metal CVD, Wiley (1994), and WS Rees, CVD of Nonmetals, Wiley (1996) ° Sr oxide precursors

Sr (thd) 2 or Sr (thd) 2 additives are usually used as precursors of Sr oxides, where thd represents 2,2,6,6-tetramethyl-heptane-2,5-dionate, and other additives can be: Polyesters, for example, RO ^ CH / I ^ Oh-R, where 2Sn ^ 6, and each of R and R 'are each an aromatic group, or hydrogen or a polyamine, for example , ΙΙ-ΝΙΤ-ΚΗΊΝΙΙΠ-Π, where 2gn S6, wherein each of R and R1 is independently an aromatic group, alkyl group or hydrogen and R "is”, Me, Et or Pr.

Sr (thd) 2 additives can include tetraglyme, triglyme, N, N, N ', N 丨 丨, N' 丨-pentamethyl-diethylene-triamine or -15- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------- order --------- line (please read the precautions on the back before filling this page) 575679 A7 B7 V. Description of the invention (4) Ν, Ν, Ν ', Ν' ', Ν'Π, Ν' ''-hexamethyl-triethylene-tetramine 〇

Precursors of Ta oxide:

The precursors of Ta oxides usually have a structure: Ta (OR) ^ (X) w, where R is Me, Et, Pr, 'Pr, Bu, j Bu ^ fBu, pentyl, or' pentyl; where X is a a- diketonate, and where l $ nS5, for example,

Ta (0 lP〇 (thd) can be used as the precursor of Ta oxide. S B T: osmium bismuth giant salt usually has the structure: SrBi 2 Ta 2 0 9 or its derivative, like: SrBi 2Ta 2_zNb 9, where 0 $ XS2

SrBi 2Nb 20 9

Sri_zBa2Ta2_yNby09, of which 0SXS1 and 0SYS2 Sr jjCa zBi 2Ta 2_yNb y09, of which 0SXS1 and 0SYS2 Sr ^ Pb 2Ta 2_FNb yO 9, of which 0SXS1 and 0SYS2 Sr pujBa zCa yPbZ $ 1 ZB2Z $ 2ZY2Ta2S OgPS2 SBT also contains the above-mentioned compounds, which are composed of one or more elements and are doped from lanthanide metals such as Ce, La 'Pr, Ho, Eu, and Yb. The precursors of the mixed solution B i, S r and Ta oxide are dissolved in a solvent or a mixed solution and introduced into the evaporator in the liquid phase. For example, this solvent contains but is not Limited to a 1 iphatic (aliphatic), cycloaliphatic (aromatic), aromatic ((aromatic) solvents, this sol may have some functional groups, such as alcohols, esters, ethers, esters, amines, ketones and aldehydes, For example, the precursors of Bi, Sr, and Ta can be dissolved in octane, nonane, decane, undecane, dodecane, tridecane, or -16- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling out this page) -0 ϋ ϋ -ϋ ϋ Order --------- Line-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed Agricultural 575679 A7 B7 V. Description of the invention (π) tetradecane, etc. A mixture of these solvents can also be used, for example, a mixture of THF, fprOH and tetraglyme in a ratio of 8: 2: 1. Similarly, THF, PrOH and polyamines Example 8: 2: 1 mixture, likewise, mixtures such as octane, decane, and pentamethyl-diethylene-triamine at a ratio of 5. 4: 1, further details are described in the recently occurring patent USSN 09 / 107,861 published in 1998, On June 30th, it was named amorphous deposited metal oxide ceramic film, which was incorporated as a reference. Evaporation process:

The precursors of Bi, Sr, and Ta oxides have been evaporated before being introduced into the CVD chamber. This precursor solution is evaporated, for example, in one or more evaporators. This precursor solution can be placed on all three precursors, or multiple solutions can be used on each solution containing one or more precursors. In a CVD process in which a single source of liquid is introduced, the Bi aromatic group is evaporated side by side with Sr and Ta oxides. Next, it is necessary to prepare a solution containing some three precursors. Another method is to evaporate Containing Bi aromatic group, and Sr and Ta oxide in another evaporator, the first method is more suitable for manufacturing SBT layer, because it is easy and deposition can be easily controlled. Several lead-in methods can be used in multiple evaporators. These precursors are stored in separate solutions, and each is evaporated in different evaporators. This vapor is mixed and then introduced into the surface of the substrate in the CVD chamber. . On the other hand, precursors of Sr and Ta oxides are stored in different solutions and mixed before evaporation, for example, by liquid introduction into the system. This mixed solvent-17- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) --.---------- ^^ 衣 -------- Order --------- Line (Please read the notes on the back before filling this page) 575679 A7 B7__ ___ V. Description of the invention (4) The liquid is introduced into a single evaporator, the precursor of Bi oxide Then it is introduced into a second evaporator. After the precursors are evaporated, the vapor phase is mixed and introduced into the CVD chamber. In another process, precursors of S r and Ta oxide are stored in a solution of the precursor mixture and introduced into a single evaporator, and the Bi aromatic group is introduced into a second evaporator. After these precursors evaporate, these vapors are mixed and introduced into the CVD chamber. In addition, the Bi aromatic group can be evaporated in an evaporator and the oxides of Sr and Ta in the 'second evaporator, however' The T a oxide precursor is replaced in two separate reservoirs to prepare a mixed solution containing S r and T a oxides at different concentrations, so that an accurately mixed S r and Ta oxide precursor can be made. . In addition, the process that relies on CVD can be referenced in one or more of the following ways: uS patent USSN 08 / 758,599, published on December 27, 1996, is called CVD using a multi-evaporator reagent supply system composed of multiple similar precursors. ; And US Pat. No. 5,536,323; US Pat.

No. 5,337,65 1; U.S. Pat. No. 5,43 1,957; U.S. Pat. No. 5,362,328; and U.S. Pat. No. 5,204,3 14. Oxidant

The precursors of Bi, Sr, and Ta oxides are decomposed by oxidative decomposition in the presence of an oxidant. O2 is usually used as an oxidant. However, effective deposition can be achieved by more reactive oxidants in the film deposition. There are improvements over time. Examples of these different oxidants include a single o2, 03, h2o2, N20, NOz (1 $ XS3), and 02 plasma. The concentration of this oxidant can be maintained between 5% and 95% of the total gas amount. 1 8-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before (Fill in this page) # Order --------- Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 575679 A7 B7 V. Invention Description (α) and Vapor Volume And flow into the CVD chamber, at least one of O2 and N20 is used in the reactor, the oxide can be supplied to the CVD chamber from an external source, such as a container, or converted into an active oxidant by molecules An active oxidant is formed in the CVD chamber and the plasma using CVD, or it is achieved by UV light, a photosensitizer, or an ion beam. 〇3 can form an oxygen reactive group, and then react with precursors of Sr and Ta oxides. This reaction may occur at the boundary layer. For example, the reactive group of oxygen is incorporated into the Bi-C bond. In the junction, or by cycling the reaction of bimolecules by electricity. When 〇3 reacts with a precursor containing a benzene ring, 03 will attack the benzene ring and cleavage the molecule from the other side to obtain an intermediate product like 〇BiBh3, which may be decomposed back to BiPh3 or The rearrangement reaction forms (PhO) BiPh 2 and the chemical properties on the substrate surface can also be affected by 〇3. For example, the amount of oxygen atom desorption may increase, or the surface's electrochemical potential and conductivity It may be changed, and O3 may affect the surface chemical properties of the Bi-containing metal oxide film grown in the CVD chamber. NO and NO 2 can already react with these precursors at the interface layer. In addition, NO and NO 2 can also be adsorbed on the surface and react with the intermediates from the decomposition reaction of the precursors, or increase this further. Chemical reaction on the substrate surface. h2o2 can react with precursors on the boundary layer or heterogeneous surface, and H 20 2 can form OH and 00H groups on the substrate, and can provide new decomposition pathways for these precursors. Che Yihua 〇2 ('〇2) by -19 such as rose bengal or below 200- This paper size applies to Chinese national standards, (CNS) A4 specification (210 X 297 mm) II ----- ----- 0W -------- Order --------- line (Please read the precautions on the back before filling this page) Printed by the Employee Consumer Cooperative of the Wisdom and Finance Bureau of the Ministry of Economic Affairs 575679 'A7 _ B7 V. Description of the invention (j) Light is directly irradiated on 30 2 and directly irradiated by 30 2 in the presence of a photosensitizer to a very active oxidant, for example, a low-pressure Hg lamp or laser mine Shoot. In order to form the gas flow of the oxygen plasma, the precursor vapor will be mixed with the oxygen plasma. In this plasma, the reactive species are single oxygen atoms, reactive molecules and 0, this plasma is before the oxidant. Generated by mixing with precursor vapor, this effective technique is to modify the CVD process method, without directly exposing the precursor to high conversion energy directly in the plasma. This comes from G. Lucovsky et al. In J. Vac, Sci. Tech. A4. 681, 1986; Van Buskirk et al., J. Vac, Sci. Tech. A10, 1578, 1992. The use of oxidants provides some benefits on the deposition of Bi-containing metal oxide films. Generally speaking, oxidants can deposit Bi oxides on substrates at low temperatures, and oxidants can also stabilize and strengthen Bi oxides at low pressures. The deposition of oxidants can also help achieve the desired phase on the deposition of Bi-containing metal oxide films. CVD process When BiPh 3 is used as the precursor of Bi oxide, the stoichiometry of the SBT film can be obtained at temperatures below 400 ° C. However, the deposition of Bi oxide can be related to the substrate, for example, Bi oxide is better deposited on Pt or Bi20 3 than Si02, Ta20 5 or SrO. This substrate-related property may lead to poor reproducibility between pieces and poor uniformity within the sample. In addition, Bi oxides may be separated from Sr and Ta oxides. The deposition of Bi oxides seems to be more than -20- This paper size applies the Chinese national standard (cns) a4 specification (2 Sichuan χ 297 mm) ---------------- ---- Order --------- line (please read the notes on the back before filling this page) 575679 A7 __B7__ 5. Description of the invention (θ)

Bi substrates are more assisted, that is, Bi oxides tend to be deposited where Bi oxides have been deposited. This surface correlation may require more precise control of CVD at low temperatures and the use of BiPh 3 as the precursor of Bi oxide. One way is to use 02 as an oxidant and increase the temperature to decompose the Bi oxide. However, a low deposition temperature is required to have good uniformity of the Bi oxide and inhibit the migration of Bi to the bottom electrode and substrate. And prevent the plug from oxidizing. Another method can add oxidants, or it can help the oxidative decomposition discussed in the previous section. For example, plasma, UV light, ion beam and thermal energy can be applied to the CVD chamber to help BiPh 3 Oxidation. Addition of other oxidants, such as 〇3, alcohol, and Η 2 0 can also be added, for example, an additional 0 2 ~ 2% 0 3 will increase the deposition rate of Bi oxide; however, too much 〇 3 It will prematurely decompose the Sr precursor. In order to prevent this reverse decomposition, the Bi oxide precursor may be evaporated in a different evaporator, and it is carried out when it is mixed with Ar, O 2 and 03. The precursors of Sr and Ta oxide are individually evaporated; and their vapor is mixed with the precursor vapor of Bi oxide. By reacting Bi aromatic vapor with O 3, the amount of this reactive 0 3 can be reduced with Sr And Ta oxide vapor is reduced before mixing. The time during which the Bi aromatic group is mixed with 03 can be controlled by processing the load gas flow rate and the pressure in the CVD chamber. Mixing of these precursor vapors can occur before entering the CVD chamber, for example, at the entrance of a nozzle 'or in a reactor, for example, in a nozzle. Similarly, 〇3 can be placed into the chamber separately, so that 〇3 will be in contact with the vapor precursor for a very short time. For example, 〇3 can be injected to the bottom through a separation ring with a nozzle point- 2 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) ---------- f (Please read the precautions on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Printing Cooperative Printing Clothing

Yikou, I-^ n. ^ Ϋ ^ 1 * Bif ϋ · * 11 n I _i ^ i ϋ I— i ^ i ϋ ^^ 1 i ^ ii Jaw _1 n Bi_l ϋ i ^ in Hi l ^ i ϋ ϋ i I 575679 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (^). In other methods, the separation of the Bi oxide precursor can be aided by chemical modification of the Bi aromatic group. For example, one or more phenyl atoms of the fluorene atom can have other functional groups, such as alkyl , Alcohol, gas-aromatic or amine groups, this substitution can provide a more efficient decomposition pathway. For example, oxy-alkyl, oxy-aromatic or amine groups are present on the benzene ring and will be activated. This ring also helps oxidation. This substrate will be heated to a temperature within the range of 300 ° C ~ 500 ° C for deposition. Appropriately, the substrate is heated to a temperature below 450 ° C. The pressure in the chamber is maintained at 0.1 ~ 10 Torr, the load gas is Ar, He, or N2, etc., the oxidant is 02, single 02, 03, H202, N20, N0j (l $ XS 3), and the oxygen plasma gas flow is all It can be introduced into the CVD chamber. The total gas flow rate is maintained at 1 and 15000 seem. Meanwhile, see indicates that the unit airflow is at the unit cc / min, which is measured under standard conditions, that is, at 0. 〇 and 1 atm. This deposition time ranges from 30 to 60 minutes. For SBT, the CVD process can be performed at different temperatures. For example, when the CVD process temperature is 430 ° C, a non-ferroelectric film in the fluorite phase can be obtained. By 600 ° C ~ 820 ° C For annealing, for example, at 750 ° C in the next hour, the film will be transformed into Aurivilius phase of ferroelectric material. The structure of this deposited film is related to many different deposition parameters, although this deposition temperature has the most important effect. For example, films deposited at lower temperatures, for example, at 350 ° C, are absolutely amorphous. Example 1 Low-temperature CVD process-Pt / Ti / Si02 / Si substrate (100nm Pt / 30nm Ti / 625nm Si02 / -22- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -------------------- Order --------- line (please read the notes on the back before filling this page) 575679 Bureau of Intellectual Property, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 ___ 5. Description of invention (Η)

Si) In the CVD chamber, a resistance wire heater is used to maintain the substrate temperature at 300 ~ 500 ° C, for example, at 430 ° C.

Bi (Ph) 3, Sr (thd) 2 (tetraglyme), and Ta (OzPr) 4 (thd) are used as precursors of Bi, Sr, and Ta oxide, respectively, and the precursors of Bi, Sr, and Ta oxide are each Do not store in THF, fprOH, and tetraglyme, each in a ratio of 8: 2: 1, in each solution, the concentration of the Bi precursor is 0.4 mole, the Ta precursor is 0.4 mole, and 0.15 Mol Sr precursors, these solutions are mixed in a liquid introduction system and introduced by a pump connected to a two-chamber fast steamer, and separated by a stainless steel ceramic mixture, the precursor solution It is evaporated in ceramic at 200 ° C, and its concentration in the gas phase is 21.5% Bi precursor, 7 4: .2% Sr precursor and 4.3% Ta precursor, and Ar is used as a load. The gas is used to transport precursor vapor into the CVD chamber. 〇2 and 〇3 are used as oxidants, 〇2 is introduced into the CVD chamber to establish the required O 2 / Ar ratio, 〇 3 is obtained in a 103 electronic discharge generator and by means of UV light absorption device. The pressure in the CVD chamber is 8 Torr, and the total vapor flow rate is between 50 and 2000 seem, for example! 〇 〇 〇 sc-cm '. The flow rate of 〇2, 〇3, and Ar injected into the CVD chamber is controlled at a concentration of 〇2 being a total flow rate of 20% to 80%, for example, 50%, and 〇3 vs. 〇2 The concentration ratio is less than 5%. By adjusting the total air flow through the throttle valve, the pressure in the CVD chamber is maintained, and the wall, the evaporation bath head, and the connection line are heated to 200 ° C to 220 ° C. The deposition time is 30 minutes. After deposition, the precursor gas is turned off and the exhaust gas is conducted with a high conductivity. -23- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ --------- Order --------- line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (》) Captured by a vacuum pump and excluded. This chamber was flushed with an Ar / O 2 mixed gas, and the substrate was heated to 750 ° C for 60 minutes or 800 ° C for 15 minutes to form a ferroelectric Aurivilius phase. Example 2 High-temperature CVD process CVD can also be performed at high temperature. For example, at 600 ° C, the precursor and deposition conditions are the same as those used at low temperature. This high temperature process results in a non-ferroelectric Membrane of fluorite phase, a ferroelectric Aurivi 1 ius phase, or a mixture of these phases. After the CVD process, the deposited film was annealed at 750 ° C for 60 minutes, or 800 ° C for 15 minutes to form a fully crystalline ferroelectric Aurivilius phase. Example 3 Multi-step CVD process A multi-step process is also used. One of the different deposition conditions is to obtain a film with a high Bi content in the first 2 to 10 minutes, and it is adjacent to the bottom electrode of Pt, and is better than other The film comes high. After the first 2 to 10 minutes, the amount of Bi oxide is increased to be introduced into the CVD chamber. For example, this is achieved by increasing the liquid introduction in the oxygen-alcohol evaporator of Bi. In this step, All other parameters in the step, and all parameters in the subsequent steps are the same as those used in a single step. When this invention is described and understood in conjunction with the detailed description, this previously described description is not limited by this invention, it is defined by the scope of the attached patent application, and other ideas, advantages and amendments are Covered in the following patent applications. Explanation of symbols 1 ... Ferroelectric layer 24- This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) '-------------------- Order --------- Wire (Please read the precautions on the back before filling this page) 575679 A7 B7 V. Description of the invention (W) 2 ... Capacitor 3 ... Transistor 4 ... Bit line 5 ... Word line 6 ... bottom electrode 7 ... drain electrode 8 ... plug 9 ... ferroelectric layer 10 ... top electrode --------------------- order ----- ---- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

575679 A8 B8 C8 D8 VI. Application for patent scope. 1 · A method for forming a Bi oxide film on a substrate. This method includes: Decomposing the B 1 oxide precursor at a temperature below 4 50 ° C to form Bi oxide, and Bi oxide is deposited on the substrate, wherein the Bi oxide precursor includes at least one aryl group. 2. The method according to item 1 of the scope of patent application, wherein the precursor of the Bi oxide is dissolved in a solution before being decomposed. 3. The method according to item 1 of the scope of patent application, wherein the step of decomposing the precursor and depositing the Bi oxide is generated at a temperature lower than 40 ° C. 4. The method according to item 1 of the scope of patent application, which It further includes: decomposing precursors of Sr oxide and precursors of Ta oxide at a temperature lower than 450 ° C, and depositing the Sr oxide and Ta oxide on the low material. For example, the method of claiming a patent scope item 1 further includes converting the film into a ferroelectric film by annealing. 6 · The method of claiming a patent scope item 1 wherein the film is deposited as a ferroelectric film. 7 The method according to item 4 of the patent application scope, wherein the method further comprises: placing the substrate in a chamber; heating the substrate to a deposition temperature below 450 ° C; introducing the Bi oxide precursor, Sr Oxide precursors and vapors of Ta oxide precursors are in the chamber; the precursors of the Bi oxide, Sr oxide, and Ta oxide are decomposed into their oxides; and -26- this paper size applies Chinese national standards ( CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I · ϋ * ιβ i · ^ i · ^ — I ϋ 11 n -HI ^^ 1 tMm ϋ —ϋ · ϋ 1 ϋ ϋ—. ^ 1 * 1 ^ — Qu s OU 8 ABCD 575679 6. Deposit the oxide on the substrate within the scope of a patent application. 8. The method according to item 7 of the scope of patent application, wherein the decomposition of the precursor includes: introducing an oxidant into the chamber; and The precursors are converted into the oxides by oxidative decomposition. 9 · The method according to item 8 of the scope of patent application, wherein the oxidant comprises at least one of 02, 03, 2202, N2O, N0. γ, where X is 1, 2 or 3 and its downstream oxygen plasma. 10 · The method according to item 9 of the patent application range, wherein the oxidant accounts for 5% to 95% of the total amount of gas and vapor flowing into the chamber. 1 1. The method according to item 8 of the patent application, wherein at least two different oxidizing agents are introduced into the chamber. 12 · The method according to item 9 of the patent application, wherein the oxidant includes at least one of 02 and ν2. 1 3 _If the method according to item 8 of the patent application, wherein the formation of the oxidant is The molecules in the chamber are converted into an active oxidant by applying at least one of plasma, UV light, thermal energy, sensitizer and ion beam. 14 · The method according to item 1 of the patent application range, wherein the B i oxide is first The formula has one of 3, 4, and 5, and the alkyl component of the alkoxy group is a component of Me, Et, Pr, 'Pr or; Bi (bi- (dialkylamino) -phenyl) 3 Where the position of the amine group is selected from both 2, 3, 4 and 5 'and where the base is 1 ^ &, £ | ;, 1) 1 :, 11: or 411; Bi (fluorophenyl ) 3 ′ where the position of the fluorine atom is selected from one of 2, 3 and 4; Bi (difluorophenyl) 3, where the position of the fluorine atom is selected from two of 2, 3, 4 and 5; -27 -This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the precautions on the back before filling this page) -mn ^^ 1 ϋ_1 · ϋ ϋ I ^ t H ϋ ·· I ί m = σ line 丨 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs π 575679 A8 B8 C8 D8 VI. Application scope & Bi (trifluorophenyl) 3, where the position of the fluorine atom is selected from 2 , 3, 4 and 5; Bi (four Fluorophenyl) 3, where the position of the fluorine atom is pseudo 2, 3, 4 and 5; and Bi (pentafluorophenyl) 3; 81 (卩 11) 3 or 81 (? 11 (1〇) 3, where R Is a fluoro group, an aromatic group, an oxyalcohol group or an amine group. 15 · The method according to item 1 of the scope of patent application, wherein the precursor of the so-called Bi oxide is selected from the group consisting of: 81 (phenyl (1〇) 3, 1 { From one of 2, 3, and 4, and wherein R is methyl, ethyl, propyl, isopropyl, or third butyl; Bi (phenyl (ΙΓ) 2) 3, wherein Rf is a pseudo-selection of position From two of 2, 3, 4 and 5, and where R · is Me, Et, Pr, ipr or tBu; Bi (phenyl (R · ") 3) 3, where the R " group is in three positions The choices are from 2, 3, 4 and 5, and R " is Me, Et, Pr, ipr or tBu; B i (tetraalkylphenyl) 3; Bi (pentylphenyl) 3; Bi ( Alkoxyoxyphenyl) 3, wherein the position of the alkoxy group is selected from 2, 3 and 4 bis, and wherein the alkyl component of the alkoxy group is Me, Et, Pr, αρ r or t Bu; Bi ( Dialkoxyphenyl) 3, where the position of the alkoxy group is selected from 2, 3, 4, and 5 and the alkyl component of the alkoxy group 傺 Me, Et, Pr, -28- Applicable to China National Standard (CNS) A4 specification (210 x 297 mm) (Please read the precautions on the back before filling in this ) # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs tl --------- line-Ψ -------- I; --------- 575679 A8 B8 Γ9, D8 t. Patent application scope ip r or 4 u; Bi (dialkylamine-phenyl) 3, in which the position of the amine group is selected from 2, 3 and 4 bis, and in which the alkyl component 傺 Me, Et, Pr , Hr or hu ·, Bi (bis- (dialkylamine) -phenyl) 3, wherein the position of the amine group 傺 is selected from 2, 3, 4, and 5 bis, and wherein the alkyl component 傺 Me, Et, Pr, Xfvm t Bu; Bi (fluorophenyl) 3, where the position of the fluorine atom is pseudo selected from one of 2, 3, and 4; Bi (difluoro-phenyl) 3, where the position of the fluorine atom is selected from 2, 3, 4 and 5 bis; Bi (trigas-phenyl) 3, where the position of the gas atom is pseudo-selected from 2, 3, 4, and 5 ter; Bi (tetragas-phenyl) 3, where the gas atom The position is pseudo-selected from the four of 2, 3, 4 and 5; and Bi (pentafluoro-phenyl) 3. 16. The method according to item 15 of the patent application, wherein the precursor of the so-called Bi oxide is (0 tolyl) ) 3, Bi (m-tolyl) 3, Bi (p-tolyl) 3, Bi (2,4-dimethylphenyl) 3, Bi (2,4,6-trimethylphenyl) 3 , Bi (4 -Third butylphenyl) 3, Bi (2,4,6-trialkylphenyl) 3, Bi (4-methoxyphenyl) 3, Bi (4- (N, N-dimethyl) -Phenyl) 3, or Bi (4-fluorophenyl) 3. 17. The method according to item 1 of the scope of patent application, wherein the film system includes Ca, Ba, Pb, Na, Fe, Al, Sc, Y, Ti, Nb, W, Mo, Ce, -28a-this paper standard applies China National Standard (CNS) A4 Specification (210 x 297 mm) (Please read the precautions on the back before filling this page) --------- Order --------- Line- -At least one of 575679 A8 B8 r «D8 t, patent application scope La, Pr, Ho, Eu, Yb, etc. printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 18. The method of claim 17 in the scope of patent application, wherein the membrane 僳 includes a compound having the formula: (Bi202) 2+ (α ^ β ⑺ 0 3w + 1), where A is Bi 3+, L 3+, L 2+ C a 2+, S r 2+, B a 2+, Pb 20 or Na +, B is Fe3 +, A1 3+, Sc 3+ Y 3+, L 3+, L4 +, Ti 4+, Nb 5+, Ta 5+, W6 +, or M 6+, where L is selected from the group consisting of Ce4 +, La 3+, Pr 3+, Ho 3+, Eu 2H ^ Ya31 +, and m is 1 , 2, 3, 4 or 5. 1 9 · The method according to item 1 of the scope of patent application, wherein || Mo Yin includes compounds selected from the group consisting of: Bi2W06; BiM03, where M is Fe or Mη; Ba2BiM06, where M is V, Nb or Ta; Pb2BiM06, where M is V, Nb or Ta; Ba3BL2M09, where M is Mo or W; Pb6 BiM018, where M is Mo or W; Ba6 BiMOis, where M is Mo or W; Pb6BiM018, where M is Mo or W KBiTi 20 6 and K 2BiNb 50 15. 20. The method of claim 1 in the scope of patent application, wherein the film pseudo-comprising includes compounds selected from the group consisting of: Bi4Ti3012, PrBi3Ti3012, Η ο B i 3 T i 3 Ο 12; LaBi3Ti3012; Bi3TiTa09; -29- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) f Printed clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy— > mmmmmm Mmmt an Bn · ϋ I ϋ I— I i_n 1 ^ 1 n If In 1 St Hi Hi HI 575679 A8 B8 C8 iD8 VI. Application scope of patents Bi 3TiNbO 9; SrBi4Ti4015; CaBi 4Ti 40 15; BaBi 4Ti 40 15; PbBi 4Ti 4015; Sr xB2i YFb zBi 4τί 40 15 ^ where 0SXS1, OSYS 1, and 0 SZ g 1; Sr2Bi4Ti5018; Ca 2Bi 4Ti 50 18; Ba2Bi4Ti5018, Pb2Bi4Ti5018; S r 2-You-yz Ca zBa yPb zBi 4 Ti50S, SYS 0X 2, and 0 $ Zg 2; SrBi 5Ti 4FeO 18; CaBi 5Ti 4FeO 18; BaBi 5Ti 4FeO 18; PbBi 5Ti 4FeO 18; Sr u_y_zCa zBayPbzBi5Ti4Fe018, among which OSX ^ l, 〇 $ YS 1, and 0 SZS 1; Bi5Ti3Fe015; LaBi4Ti3Fe015; PrBi 4Ti 3FeO 15; Bi 6Ti 3FeO 18; and Bi 9Ti 3Fe 50 27. -30- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ------ --- Line L Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, A8 B8 Γ8 D8 VI. Application for Patent Scope 21. For the method of applying for the scope of patent No. 20, where At least one element of the compound is replaced by a metal selected from the group consisting of Ce, La, Pr, Ho, Eu, and Yb. 22. The method of claim 4 in the scope of patent application, wherein the film pseudo-comprising includes compounds selected from the group consisting of: SrBi 2Ta 20 9; SrBi2Ta2_zNbz09, where OSXS2; SrBi 2Nb 20 9; Sr ^ Ba zBi 2Ta 2_yNb y09, where 0SXS1 and 0SYS2; S ru Ca zBi 2Ta 2_y N by O 9 'where 〇 $ X $ l' and 0SYS2; Sri_zPbzBi2Ta2_yNby09, where 0SXS1 and 0SYS2; and S r Ba especially Ca yPb zBi 2Ta 2-p N bp 〇9, where OgXgl, YS1, O ^ Z ^ l, and 0 ^ P ^ 2. 23. The method of claim 22, wherein at least one element of the compound is replaced by a metal selected from the group consisting of Ce, La, Pr, Ho, Eu, and Yb. 24. The method according to item 4 of the patent application, wherein the precursor of the Sr oxide is Sr (thd) 2 or Sr (thd) 2 additive 0 25. The method according to item 24 of the patent application, wherein the so-called Sr oxidation The precursors of the substance include at least one of polyester and polyamine. 2 6 · The method according to item 25 of the scope of patent application, wherein the polyester is of the formula R-0- (CH2CH20), 7-R, of which 2SnS6, and each of R and V is independently Academic, aromatic or hydrogen. 27. If the method of applying for the scope of the patent No. 25, wherein the polyamine is -3 1-(Please read the precautions on the back before filling this page) f Order -------- ά—0- ------- ml · — — This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 575679 A8 B8 C8 D8 VI. Patent application scope R-NR ''-(CH2CH2NR ") "-R ', wherein 2SnS6, wherein any one of R and R' are each independently alkyl, aromatic or hydrogen, and wherein" "is H, Me, Et or Pr. 28. The method according to item 27 of the scope of patent application, wherein the precursors of the Sr oxide include tetraglyme, triglyme, N, N, N ', Nn, N' '-pentamethyl-diethylane-triamine, and Ν, Ν, Ν ', Ν 丨 ,, Ν " 丨, NM,-hexamethyl, triethylane-tetramine is at least one kind. 29. The method according to item 4 of the patent application, wherein the precursor of Ta oxide has the formula Ta (OR) 5 _ „(X)„, where R is Me, Et, Pr, f'Pr, Bu, Bu; , 'Bu'pentyl, or' pentyl; where X is a diketonate, and where η is 1, 2, 3, 4, or 5. 30. The method of claim 29, wherein the precursor of Ta oxide is Ta (0 " Pr) 4 (thd). 31. The method of claim 4 in which at least one precursor is dissolved in a solution including at least one of aliphatic, cycloaliphatic, and aromatic solvents. The solvent includes alcohol, ether, At least one functional group among ester, amine, ketone, and aldehyde group. 32. The method of claim 31, wherein the precursors of the Bi, Sr and Ta oxides are all dissolved in the solution. 33. The method of claim 32, wherein the solution comprises THF, trOH and tetraglyme, and their respective ratios are 8: 2: 1. 34. If the method of applying for the scope of patent No. 32, where the solution is -3 2- This paper size applies to Chinese National Standard (CNS) A4 specification C210 X 297 mm) (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-βκκβ II ϋ ^^ 1 · ϋ ^ ^ i ^ i an BiBi i ^ i Hi I 1 II —— i I 1 I— i ^ i ^^ 1 11 ^ ^ 1 i ^ i 575679 A8 B8 C8 D8 6. The scope of patent application is THF, trOH and poiyamine, and their respective ratios are 8: 2: 1. 35. The method of claim 31 in the scope of patent application, wherein the solution includes at least ~ 'of octane, nonane, decane, undecane, and ten. Tridecane and tetradecane Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 6 · The method according to item 31 of the patent application, wherein the solution is evaporated by at least one evaporator. 3 7 · If the method in the scope of patent application No. 36 is used to evaporate at a temperature range of 170 ° C to 25 0 ° C 3 8 · If the method in the scope of patent application No. 36 is added to the solution vapor, and an inert gas is used. The evaporated mixture is introduced into the chamber. The inert gas system includes at least one of Ar, He and N 2. 39. The method of claim 38, wherein the mixture includes vapors of precursors of Bi, Sr, and Ta oxides, and their respective ratios are 2: 1: 2. 40. The method according to item 7 of the patent application range, wherein the oxide is deposited in a temperature range of 300 ° C to 500 ° C. 4 1 · The method according to item 7 of the patent application range, wherein the pressure in the chamber is in the range of 0.001 to 760 torr. 4 2 · The method according to item 41 of the scope of patent application, wherein the pressure in the chamber is between 0.1 and 10 Torri. 43. The method according to item 8 of the patent application, wherein an additional inert gas is added to the chamber, the inert gas system includes at least one of Ar, He, and N 2, and wherein the additional inert gas system accounts for gas Heliu-33- where the solution is from the inert gas (please read the precautions on the back before filling this page). Fee subscription ------- ---- line ------- -l ·! This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 575679 Printed clothing A8 B8 C8 D8 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10% and 90%. 44. The method according to item 4 of the scope of patent application, wherein the oxidizing agent comprises 0 2 and 0 3, and wherein the ratio of 3 / (〇 2 + 〇 3) is less than 0.1. 45. The method of claim 4 in which the oxide is deposited on the substrate within a period of 2 minutes and 2 hours. ^ 46. The method according to item 45 of the patent application range, wherein the oxide is deposited on the substrate within a period of 2 minutes and 15 minutes. 4 7. The method according to item 5 of the patent application range, wherein the film is heated to a temperature between 600 ° C and 800 ° C during a period of 5 minutes and 3 hours. 48. The method of claim 36, wherein the vapor mainly composed of the Bi oxide precursor is transported to the chamber within 30 minutes after the start of deposition and deposition. 49. The method according to item 1 of the patent application scope, wherein the substrate system includes Si, η-doped Si, ρ-doped Si, Si02, Si3N4, GaAs, MgO, 8012 03, 21 * 02 , 51! ^ 03,: 8 & 1 ^ 03 and PbTi03 *. 50. The method of claim 1 in which the film is deposited on the bottom electrode deposited on the substrate. The substrate includes a transistor therein, and the bottom electrode is connected to the transistor by a plug. coupling. 5 1 · The method according to item 50 of the scope of patent application, wherein the bottom electrode comprises at least one of the following: A metal, which is selected from 卩 1,? (1, 8, 11, 11 and 1111; a conductive metal oxide selected from Ir0%, Rh0%, Ru0z, 0s0x, Re0z, WOi, where X is 0, 1 or 2; a conductive Metal nitrides are selected from ZrN /, and WN / TaN y -34- (Please read the precautions on the back before filling out this page) f Line 丨 · This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 575679 A8 B8 C8 D8 6. The scope of the patent application is 0SXS1 and 0SYS0.7; or a superconducting oxide selected from YBa2Cu3〇7_x, and Bi 2Sr 2Ca 2Cu 30 10 〇5 2 The method of applying for the scope of patent No. 50, wherein the bottom electrode is a pt electrode. 5 3 · The method of applying for the scope of patent No. 50, wherein at least one first interposer is provided between the bottom electrode and the plug, the The first interposer includes at least one of an adhesion layer and a diffusion barrier layer. 5 4 · The method according to item 50 of the patent application scope, wherein at least one second interposer is provided between the bottom electrode and the metal oxide film, The second interposer includes a seed layer, a conductive layer, and a dielectric. At least one layer of the mass layer. 5 5 · The method according to item 50 of the patent application range, wherein the plug is connected to the bottom electrode and the drain of the MOSFET ferroelectric field effect transistor, and the plug is mainly composed of W or Si composition. 56. The method of claim 50 in the patent application, wherein the film is used as a thin ferroelectric film of a ferroelectric capacitor. 5 7. The method of claim 50 in the patent application, wherein the film is used as a The ferroelectric film of the ferroelectric memory is used. 5 8. As the method of applying for the scope of the patent No. 50, wherein the film is used as the ferroelectric film of the ferroelectric field effect crystal. 5 9 · As the method of applying the scope of the patent, No. 8 The substrate is rinsed with a mixture of an inert gas and an oxidant before being exposed to the vapor of the metal oxide. 60 · The method according to claim 8 in which the substrate is exposed to -35- this paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs t --------- ^ — --------- 1__ — — — — — 575679 A8 B8 C «D8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. After applying for the patent scope, the precursory vapor is washed with the mixture of the inert gas and the oxidant. The material was subjected to at least one of the methods of thermal heating, decomposition, and accretion at least twice. 62. The method of claim 8 wherein the substrate is removed from the chamber and returned to the chamber after being processed in at least one intermediate process. 63. The method according to claim 3, wherein the composition of the precursors in the mixture varies with the substrates deposited in the chamber. 64 · Method No. 38 of the scope of patent application, wherein the composition of the inert gas in the mixture is changed according to the different substrates deposited in the chamber. 65 · Method No. 8 of the scope of patent application, The composition of the oxidant varies with the substrate deposited in the chamber. 6 6. The method according to claim 7 in which the deposition temperature is changed depending on the substrate deposited in the chamber. 67. The method of claim 7 in the scope of patent application, wherein the pressure in the chamber varies with the substrate deposited in the chamber. 68. The method according to claim 7 in which the substrate is heated at least twice at a temperature of less than 450 ° C. 69. The method of claim 7 in the scope of patent application, wherein the substrate in the chamber is heated in the presence of at least one of 02 and 03 at a temperature lower than 45 ° C. 70. In the case of scope 7 Method, wherein the substrate in the room is heated at a temperature higher than 45 0 t and is at least one -36- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ） — II ------------------ Order (Please read the precautions on the back before filling this page) 575679 A8 B8 C8 ____ D8 6. The scope of patent application is in the presence of 02 and 03. 71. The method according to item 8 in the patent claim, wherein the precursor, the oxidant and the inert gas vapor including at least one of Ar, He and N 2 are in a standard state at 1 ml / min to 15,0 A total flow of 00 ml / min was introduced into the chamber. 72. The method of claim 38, wherein at least one of the precursors of the vapor is mixed with 03 before the vapor is transferred to the chamber. 73. The method of claim 72, wherein the vapor of the Bi oxide precursor is mixed with 03 and mixed with the vapor of Sr and Ta oxide. 74 · —A method for forming a film on a substrate, the method comprising: heating the substrate to a temperature lower than 45 ° C. and introducing vapor of a Bi oxide precursor into the substrate, wherein the Bi oxide precursor is Including at least one kind of aryl, the precursor is decomposed on the surface of the substrate to form a Bi oxide, and the Bi oxide is deposited on the surface of the substrate. (Please read the precautions on the back before filling this page) -------- Order --------- Line 1 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-37- This paper size applies to China National Standard (CNS) A4 (210 X 297) Mm)