TW200906836A - Raw material for forming a strontium-containing thinfilm and process for preparing the raw material - Google Patents

Abstract

The present invention provides a raw material for forming a strontium-containing thin film of a cyclopentadienyl-based strontium compound, which is in the liquid state at room temperature to 50 DEG C., can be purified by distillation, present as a monomer, has high vapor pressure, and suitable for mass production, and a process for preparing the same. Sr[C5(CH3)4(C3H7)]2 is prepared by reacting Na[C5(CH3)4(C3H7)]2 or K[C5(CH3)4(C3H7)]2 with SrI2 in THF to produce a THF adduct of Sr[C5(CH3)4(C3H7)]2; evaporating THF and extracting the residue with toluene to give a toluene solution; evaporating toluene and drying the residue under reduced pressure; and heating to 100 to 160 DEG C. in vacuo to dissociate and remove THF and distilling.

Description

200906836 IX. Description of the invention: [Technical field to which the invention pertains] em i c has: a method suitable for chemical vapor growth (Ch below 二 Γ "

Laye / ^ no) or atomic layer stacking method (Atomlc

*To indicate) the formation of a raw material compound containing ALD and the following

The SmO of the high dielectric constant of the method is to be used as a high-product semiconductor device; B-electrode T: second-class, f-phase is discussed as an electrode of a ferroelectric film. 1 u〇3 film raw material = forming the film containing the film

nH19〇山; The following is recorded as s^(-/金斤戊) (Sr(C However, expressed by h (dPm)) ° Vapor pressure system 0. 1T〇rr/2 2;,, Emperor " The trimer is therefore a problem. The d 1 C is very low and has a thermal decomposition that will start when it is above A LdH^3 0 C. Therefore, the method of the Putian method is not only difficult to produce at the same time. The problem of thermal decomposition of control. "And therefore, there must be a kind of vapor pressure compound which is more vaporous and hot.", Dehua is highly reactive. For example, the candidate compounds can be enumerated as follows: 200906836 of the compound (5曱%*戍 chain (Sr[c5(CH3)5]2; the following is represented by Sr Cp 2). Here, Sr Cp% is not diethyl ether "c 2H5) 2〇; An adduct which has been coordinated, such as t 2 )) or tetrahydrofuran (cm Ο; hereinafter referred to as THF). Since the above-mentioned adduct has low heat stability and emits an adduct at the same time as heating and is thermally degraded, it is not possible to form a stable vapor, and since the body contains oxygen atoms, oxygen may be supplied by self-decomposition. Raw materials for ALD. On the other hand, since the srcp % of the non-additive is a monomer, the vapor pressure is the highest among the organic Wei compounds, and the water has a transient reaction suitable as a raw material of the ALD method, and = It can be easily dissolved in an organic solvent by the influence of five methyl groups. The inventor of the present invention has a manufacturing method of SrCp%. U35 However, since SrCp% is a melting point 2 〇7t, and in the line of fine = 'in the = method of making ' ' must be by sublimation operation; into the " yue, and, because it is a very small amount of oxygen, water metamorphism of the same moon beans, so must be processed High-priced equipment and careful operation., Inflation 2 gas = high steaming (four) system and easy to carry out, and the handling of the clothes under the brother, must have a kind of room temperature ~

A compound in a liquid state at a temperature. C For gas enthalpy: There must be a liquid compound which has a bismuth-like, pentadienyl-based sulphide, and which is not added to the fascinating, red, and sputum pressures, and has an easy The basis of mass production. 200906836

lilL

It is made in the raw material to make the succinyl-diketone ruthenium complex SS Ss, however, it contains Na or K of several PPm in the metal S r , and Na & K. Force 3 has a number of PP into 'since S r C p % (four) red material ^ combination; the following high to indicate;, = 1 (/ Η〇 5 (hereinafter referred to as KCP *) and other metal compounds to form, so crude The composition contains a large amount of Na or a smear. It is close to and difficult to obtain and there is no trait due to the β-diketone-based complex and sj·〇p: at room temperature, so the distillation is utilized. It is difficult to refine the N or the size of the raw material from the raw material. Therefore, in the raw material for forming a film containing ruthenium, it is difficult to apply the content of Na and K at 5 〇 ppb or less to CVD or ALD. The respective contents of Na and K are the following raw materials for forming a film containing ruthenium. Therefore, the inventors believe that among the commercially available cyclopentadiene compounds, a tetramethyl group having a structure similar to pentacyclopentadiene can be used. N-propyl) cyclopentadiene (C 5 (CH3) 4 (CsHt) H) to synthesize a compound of bis(propenylcyclopentadienyl) fluorene (sr[ C5 ( CH3 ) 4 ( C3H7) ] 9s r[ C 5 (CH 3) 4 ( C 3 H 7 )] 2 ; the following is preferably represented by sr ( pr M e 4 C p) 2 ) S r ( P r M e 4 C p ) 2 It is disclosed in the European Patent No. 6 4 5 6 5 6 and is registered as a compound of CAS No. 8 8 2 9 〇6-98-2. 29 Also, in "MOC VD & C VD P recurs 〇rs ” , S trem Company, [9 9 g year, c ν D workers / 200906836 99, p. 22 ' reveals an addition of 1,2-dimethoxyethane (CH3〇) to Sr (PrMeaCp) 2 c2H4〇CH3; the following compound represented by DME. However, in the above-mentioned European Patent No. 1 6 4 5 6 5 6 , it is only disclosed in the table of the seventh embodiment, by indium triamide When I CVD with monoethyl hydrazine as a raw material, the I nas film is grown at 600 ° C. 'Sr (P r μ e 4C p ) 2 with a catalytic amount (< 2 5 mol%) Coexisting, and Sr (PrMe4CP) 2 is added as a micro-catalyst, and substantially does not contain S r in the film, and the method or physical property of S r ( P r M e 4 C p ) 2 is not disclosed at all. In the aforementioned "MOCVD & CVD precu 1 sors, Strem, 1999, CVD 1 1/9 9, p · 2 2, no unadded sr (p rMeeCp) 2 was also disclosed. The cyclopentadienyl ruthenium compound is a compound obtained by adding a compound obtained by adding an ether, and is not difficult to synthesize by a domain, and it is not easy to remove the added ether. Therefore, the manufacturing method, physical properties of gs r (P r M e 4 C p ) 2 have not been clarified so far, and a film containing sr as a main component as a raw material has not been formed, and 'S r (P rMe4Cp) In the production method of 2, the ether compound used and the method of removing the ether become important. Further, in the material for forming the semiconductor thin film, even if only a slight amount of enthalpy is formed: the electric field unevenness at the semiconductor interface is generated or the conductive film is etched, it is necessary to make the organic error compound The concentration of N a is close to 〇' and ^ must be the same. [Description of the Invention] 200906836 The use of two and the same: the purpose is to provide a raw material at room temperature ~ 5: 〇c 'u used to form a film containing bismuth and high vapor pressure, easy mass production and refinement, as the monomer Xiao It is produced in the middle of the product and the material is obtained. Second, the purpose of Ming also provides a film that can reduce the yttrium contained in summer. The third method. Further, the object of the invention is to provide a method for producing the above-mentioned compound (Ρΐ:==in the raw material of the raw material system S r containing κ = κ = :), the preferred one is 5 〇 ppb. The following: 造方: The preparation of the raw material of the film is taken from S r ( pr M e 4 c Ρ ) 2 , : P. The propylene tetrahydrocyclopentene (hereinafter referred to as Na (PrMe4C, to the table) Or a procedure for the THF adduct of potassium tetrapropylcyclopentadienide (hereinafter P) and butterfly (W(10)Hd Gu:1; ; r M : 4 CP ) 2; steaming.. + and hunting is extracted from toluene to make a stupid Procedure for solution; Sacrifice I field IV, detoluene and dry under reduced pressure ~16... and removed after _;;:: Sr (pr = 4C) used to form the raw material of the film containing the pin of the present invention P) 2 is a liquid compound suitable for mass production, and can be obtained by appropriately the manufacturing method of the present invention. 200906836 & 升 y y film containing yttrium Me 4 C p) 2 S r of the material (pr 2 is due to the high gas pressure of the crucible and "the liquefaction of the base distillation is one, and the properties under the dish are liquid. Therefore, the trait of the tomb distillation 4 Q ta main > Yab is Body, material, can be greatly corrected =: know the content of the film containing K and the content of K. Low side; + conductor characteristics have a large impact on the N a so the right to use the Sr (prMe 1] 2 ' obtained by the present invention The content of the Na&K content can be reduced by the cv D method or T^b. [Embodiment] The present invention will be described in more detail below. The present invention relates to the formation of (4)_(pr M e 4 cp ) 2 〇" S r (P r μ e 4 Γ η Ί M + M e 4 υ Ρ ) 2 which is S er is the starting compound, which can be obtained by the manufacturing method of the present invention as appropriate. Specifically, via the following Procedure, obtain §1_(PrMe CP ) 2 ' ie: react N a ( P r M e 4 C p ) or κ ( pr Μ\4 aCp) with S r I 2 in THF and generate sr (pe ^iCp) 2 THF adduct procedure; steaming hall to remove Ding ρ, and by toluene extraction to prepare a toluene solution; steam | leaving to remove toluene and drying under reduced pressure; and heated to 1 under vacuum 〇〇~丄6 〇°C ' and the procedure of distillation after dissociation to remove THF. The manufacturing procedure is described in order below. Na (PrMe4Cp) can be obtained by a known method such as the following method, that is, commercially available propenylcyclopentadiene (c 5( c H3) 4 ( C3H7) Η; alias: tetramethyl (positive C) Base) cyclopentadienyl) 10 200906836 (manufactured by Stra em, aifa "manufactured by sar, etc.) in a method of reacting with N a N H 2 in liquid N Η 3; or a method of reacting with Na Η in TH or DME . 1. K (P rMe4Cp) can also be obtained by the same method. Next, Na (prMe4Cp) or K (P rMe4Cp) and anhydrous S r j 2 obtained by the above are dissolved in s r (p『

In the THF of the synthesis reaction solvent of Me4Cp) 2, the synthesis reaction proceeds easily, and an S r (P rMe4Cp) 2 (butyl HF) addition product is formed. Further, when DME is used as the synthesis reaction solvent, the (P rMe4C p ) 2 (DME) addition product can be easily produced. However, as shown in the following Comparative Example, DME is not suitable because the DME cannot be easily removed afterwards. . Further, when diethyl ether is used as the solvent, the solubility of the reaction raw material is small, the reaction rate is low, and the volume efficiency is poor, so diethyl ether is also unsuitable. After the completion of the synthesis reaction, the butane HF solvent is distilled off, and the S r (PrMe4CP) 2 (butyl HF) adduct is extracted by toluene, and the adduct is sufficiently dissolved by toluene, but the by-products are either Potassium sulphate does not dissolve at all - so extraction is easy. The benzene solution is distilled from the benzene solution to remove the benzene and dried under reduced pressure. Thus, a 3 r (P ^ 64 ^ ) 2 ( butyl 1 ) adduct is obtained, and the melting point of the THF adduct is about 1 3 〇. If the adduct is heated to 1〇〇~16〇 under vacuum of 〇.〇〇丄~〇·丄丁◦ r r. 〇, the inside of the kettle will form a molten state, and the THF that has been dissociated will accumulate in the cryogenic separator. If the 200906836 in the separator increases: by 0.01~ Γ, ◦ 1 1 in 160~18 Line operation, steaming I leave S r ( P r M e 4 LP ) 2 0

According to the Sr (PrM-cured viscous liquid) obtained in this way, the film obtained by the above method 31, (prMncp) recorded oxide film, sulfide film D, etc. Or ALD method to form a stable

It can be p)2. The following Sr (PrMe4C contains the K and Na obtained by the manufacturing method of the present invention;:: two (P... core) "乍 as a raw material, and forms Sr containing calcium; cliff a, Sr) Ti〇3 When the film, the SrRu〇3 film, etc. have a d-money, the supply method of Sr(PrMe4Cp)2 which can reduce the content of _tI^Na can be reduced = Sr (PrMe4Cp)2 is heated to the helium gas foaming Make it the carrier of the hydrocarbon solvent and use the liquid "quantity: amount? Enter = and use 13. ~35. . . The gasifier makes it full. Chemical

The thermostat 2 foaming method is used to correct the r (PrMeiCp) 4, and the cylinder thereof is limited to the temperature of the following examples, and can be at 1 3 〇~3 5 CTC B ° and then the carrier gas at this time is an inert gas. Yes, and in addition to A 200906836: two can use N2, He. x, when the flow rate is too small, it is also blood-rolled, and if it is too much, it is dissolved in the cylinder, so it is preferable to dissolve S1' (PrMe4Cp) 2 on the steamed spot of the raw material, which is 3〇~5〇〇 In the solvent, the pressure is reduced by 4, and the mail is transported by the mailer, and the temperature of the gas is at the temperature of I, as long as it is 5 0c heart; =: the viscosity of the target circumference can be detected by "right"; The danger of blockage inside the device. Further, when the agent is preferably used, the solution having the highest solubility can be used, and it is not limited to ',, and is low in hexane or octane. Or, it is also possible to use a vapor of titanium compound of the mountain, "(;=) (, 〇; =," 4 temple titanium vapor and oxygen, ozone ^ (NE t2) followed by VD method or ALD method to make SrT = paste 'Yes, if, in Sr(PrM ":. rMe4CP) ? base gas, she TP) 2 hot gas added B "P (〇tBu), ', T r sub-use Tl (〇ιΡ〇4, Τΐ 4 , T i (N』t / NMe2) 4, T i (NE tMe ) 匕t 2 ) 4 荨 sharp compound * & For oxidant, you can use ^ read gas, ozone, water so T1 〇 3 film. CVD It is produced by ALD or ALD (Ba, in addition, if S r ( p ^ M ep base gas and oxygen C 2 vapor and Ru (E agent), CVD method, A, water, etc. can be used as oxidation. Example ALD to produce SrRu〇3 film. 200906836 The invention of the present invention is more specifically described by the following examples. [First Embodiment] Manufacture of S rfp Ayr 1 ( P r M e 4 C p ) 2 In a flask with a thermometer, _ sub, and a population of m, after vacuum argon substitution, i Λ t ° ° - eight set left into dehydration and deoxidation ΤΗF600 and a (P rMe4Cp) 75g (〇·4〇莫耳) And = two will U-Wall water-cooled and added sr" Powder 7 2 g (〇. 2 1 旲 ear)' and stir for 4 hours at 4 〇c. 〇其"'人' & desolvent under reduced pressure 'drying and adding dehydration and deoxidation 曱 stupid 6 QQ m 1 'and the extraction operation by heating the sandalwood mixture, after standing, filtering and obtaining the permeation, the liquid 4 is self-filtered, the liquid is decomposed and evaporated under reduced pressure, and dried under reduced pressure at 10 〇 <3, A lighter color solid (decompression dried product) of 8 gg.

The solid is placed in a vacuum distillation device and maintained at 1 1 〇~1 6 〇<3/〇.1~〇.〇1丁〇11^, hourly, HF HF adduct τHF will slowly detach and accumulate in the cryo separator 8.1 g. After slowly raising the temperature and removing a trace of the preliminary distillation crystal, a pale yellow viscous liquid of 6 1 g of the main fraction was obtained at 170 180 C/0.1 to 〇.〇iT〇rr. 0 0 The viscous liquid is again injected into the high-vacuum distillation apparatus, and is kept for about one hour under the work of 〇1T〇rr, and a trace amount of residual THF is removed, and at 1 7 〇~; [8〇 °c /0.01~Q.lTorr to obtain 51-6 g of light yellow viscous liquid (one steamed product).

The 5H-sub-distillate was identified as S r (P r Me4Cp) 2 (〇·136 mol) in the results of the analysis described below, and the yield thereof was 68% with respect to Na (P 14 200906836 rMe4Cp). The following methods and results of the identification analysis and physical property evaluation of the steaming products are shown below. (I) Composition analysis The results of ICP emission spectroscopic analysis of the liquid obtained by wet decomposition, the S Γ content is 2 〇 . 7% (theoretical value 2 丄. 丄 5%). Further, in terms of impurities, Ca = 190 Å, Mg &lt; 50, Ba = 1 Å, Na &lt; 50, K < 50, Cr &lt; 50, K e &lt; 50, Cu &lt; 50, Ni &lt; 50 (unit: ppb ) 'Confirmed as southern purity. (b) iH - NMR 〇Η - NMR) Determination conditions (device: JN Μ - ECA 4 0 0 (400 Μ Η ζ), solvent: c 6 D 6, method: 1 D) The results of the measurement of the secondary distillate were compared for the purpose of comparison. The second graph shows the results of the reduced-pressure dried product. Consider the ratio of the position of each signal in the measured spectrum of the first and second graphs to the number of Η, S r (P r M e 4 C ρ ) 2 and the number of HF HF, for 6 H (ppm) The attribution is as follows. 2.01 (s), 1.97(s) 12H: leave c5 (C Dan 3) 4 one of C3H7 CH3 two and close CH3 two 2. 3 9 ( t ) 2 H : C den 2 C Η 2 C Η 3 1 . 3 6 ( m ) 2 Η : ΟΗ2〇ϋ2〇Η3 0.92 (t) 3 Η : C Η 2 C Η 2 C H3 3.14(t), 1.21(m): one of THF 〇 c dan 2 C Η 2 C Η 2 C Η 2 - — 15 200906836 According to the measured spectrum shown in the first figure, the number of moles of the THF added to the sr 1 molar is (0.348 + 0.437) / (23 . 562 + 4. 131+4 · 136 + 6" 3 8/8 = 〇. 〇9, the average chemical formula constitutes sr (ρ r M e 4 CP ) 2 (THF). Q 9, although THF is slightly coordinated, however, It can be regarded as sr ( P r M e 4 C ρ ) 2 on the solid shell. In addition, according to the measurement optical reading shown in the second figure, the vacuum drying system is added to the S r 1 molar τ HF molar number. (2.076 + 2.04 6)/(11·296+1.981+1.890+3) X 38/8 = 1.〇8, the average chemical formula constitutes sr (pr M e 4 Cp) 2 (THF) n and two relative to S r (P rMe4Cp) 2 (THF) s s sr contains a theoretical value of 18. 〇 2 %, the S r content of the reduced-pressure dried product is 18.1%. According to this 'presumed decompression dry line plus About one T HF S r( P iMe4Cp) 2 〇 (3) Properties and melting point The primary retort is slightly yellowish and is a very viscous liquid at room temperature with a viscosity of about 10 〇〇P. (4) Thermogravimetry /thermal difference analysis (τ G - DTA) 疋 measurement conditions (sample weight: 2 4 . 4 〇mg, gas environment: r atmospheric pressure, heating rate · 1 〇. 〇 deg / mi n) two = three pictures show twice For the comparison of the results of the distillation, the fourth graph shows the results of the vacuum drying product. According to the TG-DTA curve shown in the third and fourth figures, the second 200906836 distillation product is near 160 °C. There is no reduction in THF. It is estimated that THF does not exist, and it will evaporate by 9 7% until it reaches 300 °C. Therefore, the short-term help of 3Q 0W does not thermally degrade, and it can be confirmed that there is LD method or CVD method. The thermal stability required for the raw materials. (5) The result of the vapor pressure gas saturation method is 〇.丄τ 〇r 7 〇 it. (vi) Density Density is 1.2 g / c nr3 (3 〇.〇). (7) The solubility of each solvent with respect to 1 L at room temperature is 35 〇g with respect to toluene, 2 8 〇g relative to THF, 70 g relative to hexaxane, 7 octane relative to octane 0 g. Accordingly, it was confirmed that it was sufficiently dissolved in the sputum, and it was also sufficiently dissolved in octane or the like. 1. [First Comparative Example] The solvent was prepared using DME Sr (prMe4 c P ) 2 in a 3 〇〇m 1 two-necked flask equipped with a thermometer, a stir bar, an inlet, and a reflux, after vacuum argon replacement. Inject the dehydrated and deoxygenated TH F "ml" with Na (PrMe4Cp) 16g (〇. 〇86 Moule) and dissolve, and the flask was water-cooled and added S r I 2 powder 1 5 . 5 g ( 〇. 〇 4 5 Mo The ear is stirred under reflux for eight hours. Next, 'desolvation under reduced pressure' is followed by addition of dehydrated deoxygenated toluene 2 0 〇m 1 ' and subjected to extraction with heating and stirring. After standing, it is filtered and obtained. The filtrate is transparent, and the toluene is evaporated from the filtrate under reduced pressure. 17 200906836 Removed and used as 1 0 (Tc is dried under reduced pressure, although it is a pale yellow mucus at first) - but it can be obtained in the future. 5 g. Inject the solid into a high vacuum distillation unit and keep it for one hour at the time of 丄X τ 〇rr, at the time of 丄X τ 〇rr, at this time D Μ E addition D Μ E will slowly detach and accumulate in the cryo-cool separator 1.2 g. Slowly warm up and remove At the beginning of a very small amount, 70~175 to 0.1~0.01T..., the main crane system = light yellow solid which is solidified with liquid 3 and solidified at room temperature (melting point about 50~80C) (-- steaming product) 14 . The solid is poured into the high-vacuum steaming device again, and heated for 160 hours after 160 ° /〇.1~〇.〇1丁〇1", and then 'Yi丄7◦~175Ϊ/ 0·〇1~〇.1T〇r“Under, the main (four) obtains a pale color solid which is solidified by liquid evaporation and solidified at room temperature (the melting point is about 5 〇~8 〇. 〇(second steaming product M The measurement of i Η R and TG-DTA was carried out in the same manner as in the first example.

(1) 1 Η — N M R The fifth graph shows the measurement results of the secondary distillate. For the ratio of the position of each signal in the measurement spectrum of the fifth graph to the number of s r (P rMe4Cp) 2 and DME of Η, 6 H ( p p m) is assigned as follows. 2 . 1 5 ( s ), 2 · 1 2 ( s ) ]; 2H : leaving Cs 2.47

Cii Mountain - C3HaCH3 two and close CH3 two t) 2 Η : C H_ 2 c Η 2 C Η 3 18 200906836 1.63(m) 2H:CH2CJi2CH3 1 . 0 8 ( t ) 3 H : CH 2 CH 2 C Us 2 . 6 9 ( t ), 2 . 5 9 ( m ) : D Μ E of C ϋ 3 0

Cii2 Cϋ2〇Clia According to the measured spectrum shown in the fifth figure, the number of moles of the DME of the secondary distillation product added to S r 1 Mo is (2.92 1 + 1. 9 6 1 ) / (11 .726 + 1 .945 + 1 . 901 + 3)x 3 8/10 = 1 .〇〇, the average chemical formula constitutes sr ( pr μ e 4 ί. Cp) 2 (DME)i, 〇〇. Further, a signal due to a large amount of impurities can be seen, and it is presumed that thermal decomposition of the adduct is generated in the heating distillation. Further, the theoretical value of Sr (PrMe4Cp) 2 (DME) 12 S r content is ί 7.3.7%, and the analysis value of s r content of the secondary distillation product is 18.2%. According to this, in the vacuum heating distillation operation, it was confirmed that DmE was difficult to separate from the D Μ E addition body.

1: (2) TG — DTA The sixth figure shows the measurement results of the secondary distillate. According to the TG-DTA curve shown in the sixth figure, the behavior of D Μ Ε detachment was not found, and it was presumed that most of the evaporation was directly in the state of the DME adduct. ^,, lfI - NMR and D - G - DT A measurement results can be confirmed, even if the heating system is heated, DME will not be detached, and most of them are made into DME adduct and vaporized. That is, if DM E is used as the solvent and the method of the D M E addition is used, the pure S r ( p r μ e 4 C p ) 2 cannot be obtained. Therefore, it is difficult to produce pure S r (p rMe4Cp) 2 from commercially available Sr (PrMe4Cp) 2 (D] VIE). [Second Comparative Example] The raw material was produced in a 1 L three-necked flask equipped with a thermometer, a stir bar, an inlet, and a gas outlet using S c Cp% of Na Cp*, and then dehydrated and deoxidized THF 7 5 取代 after vacuum argon substitution. m 1 and N acp*7 9 g (Q. 5 Q mole) and dissolved, and the flask was water-cooled and added with sr 12 powder 9" (Q. 2 4 6 mol) and at 2 5 to 4 CTC Stir for twenty-four hours. 'Q, person, square; desolvate under reduced pressure, add dehydration and deoxidation - 〇〇m 1, and carry out extraction operation by heating and stirring, let stand and take *clear filtrate And the toluene is subjected to decompression base 3 from the filtration and liquid, and dried under reduced pressure at 1Q, if it is in the handle box ί powder 98g. If the second work enters the 仃籾ping, the yellowish loose powder can be obtained. ^华器, and at 14〇~i8〇V〇. 〇Γ Γ下仃 — — 次 次 次 次 次 次 次 次 次 次 次 次 次 升 升 升 升 升 升 升 升 升 升 升 升 6 6 6 6 6 6 6 6 亥 亥 亥 亥 亥 亥 亥 亥 亥 亥 亥And in the 1 4 0~1 white sublimation product for the second sublimation, and obtained the pure § hai second sublimation product of the community 曰CP% (0. 162 = the following knife As a result of the analysis, it was identified as Sr 9%. The ear was 'yield relative to N a C p * was 6 20 200906836 to obtain the solid of the benefit, and the first embodiment was the same as the composition analysis of the optical analysis. As a result of NMR, the average chemical formula can be estimated as follows based on the ratio of the § content analysis value to the total number of S r CP% signals of the -NMR and the number of H numbers of the THf^) number.

HF_Dry product: Sr content 19,7% SrCp% (T

H F sublimation: s Γ content 2 2 · 1 % s r c

P

T secondary sublimation product: Sr content 25.3% SrCp% mass system liter, 1 CP luminescence spectroscopic analysis result, hetero-r1°., K&lt;5°, Cr&lt;5〇, F J50 (; &lt; Q ' N 1 5 0 (unit: ppb), compared with the first case, the 'Na content is greatly increased. 嶋乐-贯施造[The third comparative example] raw materials use KCP\S r Cp% of the system 11吏 with KCP * Instead of N a CP *, except that _ Μ Μ - ratio = the same method, the yield of the raw material using the same molar amount of = 2 is 65% with respect to 仄〇0*.

The same as the first embodiment, the composition of the secondary sublimation luminescence = analysis of the impurity and the analysis of the impurity using the value of 1 CP a 1 7 is 2 5 . 〇% (theoretical value 2 4 . 0 ^ _ shell system C a = 3 0 0 〇,M g< 5 〇,b 200906836 100 0 'Na&lt;50,K=li〇〇,Cr&lt;5〇, e&lt;5〇'Cu&lt;50'Ni&lt;5〇 (unit: ρ ρ b ), f is much larger than the first embodiment. The fourth comparative example S r (dpm) 2 is manufactured by a thermometer, a mixing impeller, and a reflux device. In a Ui丄 four-necked flask, injecting toluene benzene 3 5 〇m丨 after vacuum argon substitution, which is incorporated into dipentane pentane (dpmH) 65. 6g (35 6 human ears), metal S r 7 · 8 g (8 9 m millimolar) and reacted under reflux for 24 hours, at which time the metal piece disappears: , see 讦, P m Η distillation removes the second, and the solvent is distilled off under reduced pressure. And unreacted ^, then at a temperature of 130 ° C, 〇 · 〇 5 T 〇rr a small amount of dpm Η. In the residue, 34g was injected into the high vacuum steaming device, and at 23 :) C7 〇〇 2 Τ〇 1] under the steaming crane, and take (Dp m) 2 3 ◦ g. p is the same as the first embodiment, and the result of the impurity analysis of the analysis, bit: ppb), is compared with the first multi-zero for ICP luminescence: a, 92 〇, κ = 89 〇 (single λ embodiment) The contents of M a and K are greatly changed to e 4 C p ) 2 and the formation of S r T i 〇 3 film by pr μ ALD method is used by [second embodiment] (at 170 ° C) Argon (ar has s cylinder (A) obtained by the first embodiment foaming, and at 4 〇 cm will be filled with τ i (〇ipr gas 10 〇sccm will fill r (Pr) VIe4Cp) 2 The steam is bubbled with the cylinder (B) of argon (Ar) gas 100sc)4, and 22 200906836 square; the cylinder (C) filled with water is bubbled with argon (Ar) gas 5〇scc m, and the gas system is flushed. Let a Γ 2 〇〇s ◦ cm flow, and pulsate for one second and rinse for three seconds for ALD operation. Place the substrate temperature 3 〇〇〇C2S χ substrate in the ALD chamber with a pressure of about 5 τ〇r 1 and The S r period of (A pulsation-flush-c pulsation-flush) and the T i period of (B-pulse-flush-c-pulse-flush) are alternately performed for each cycle, and the thickness r of S r T is obtained. i 〇3 film. [Third embodiment] sr (formation of SrTl〇3 film of p rMe4 ald method) (2) Heating heater heater for heating by wafer having a gas introduction port The wafer is set up by the film forming chamber of the lifting mechanism, and the film is formed by the pumping heater, and the chamber is held at 16 〇. Further, the load heater is set to 3 2 CTC to form a wafer temperature of about 2 〇.

Using the transport arm, the 31 wafers of the diameter 3 are transferred from the transport system to the plate heater, and then the argon (a『) = "S c cm is circulated" and borrowed. The temperature of the wafer is raised by the pressure regulating valve to keep the indoor pressure at 1 ◦ rr.

The S Γ obtained by the first embodiment (p M i〇〇g is filled in the foaming cylinder (4) and held at 16; wide) 2, and the body milk system makes argon (A r ) gas 5 0 s C c Day = heart) 2 steam. Again, will be filled in

The cylinder (B) of (1 P r ) 4 is maintained at 4, and argon (A 1) is rolled 2 〇〇 3 〇 0:] 11 to circulate and foam, and at the same time, butyl ^ (〇土 23 200906836) is used as water The oxidant is kept at sccm (c flow 2Πη. The outlet side 5 is again set-temperature mass flow meter and the ϋ2〇 gas seek is used again, and the flushing gas system uses A r 2 〇 to each = material supply (hereinafter referred to as pulsation) and During the flushing or rinsing, the chamber performs the following ALD operation. 'Because of the gas flow in the new test, the earth force B: 0 /1 τ 战 脉 A A. 〇· 3 T 〇rr, pulse n. ?τ· 4Τ〇 Γ Γ 'Pulsating C: 0. 5To rr, Flush: 2 9『cf ^ F. During the ALD operation, the crystal system is kept at about (4) ( (New-flushing-C pulsation-flushing) 0-shaped 幵^ For the monthly period L (B pulsation-flushing-C pulsation-flushing), the total period of T1〇 is 7 7 cycles, and constitutes S r O/T i 〇 2 weeks m.· 3 'Specifically' will (A Pulsation-flush-C pulsation-1: cycle, (B pulsation-flush-C pulsation-flush) 2 cycles, pulsation-flush-C pulsation-flush) 2 cycles, (B pulsation-flush pulsation 1 wash) cycle - a series of programming For the time, it is reversed ten times to form a sr T i〇3 film with a thickness of 5 nm. When the composition of the formed film is investigated by XRF (fluorescence X-ray analysis) method, 'S r/T i = 1 · 4. When the film is formed at the beginning of S r ( P r M e 4 C p ) 2 and the film is operated at 25 丨g (4), the average film thickness is 5.3. 5A and 50.3, the standard deviation of the intima thickness distribution is 6%. 6% and 1.3%, the standard deviation of the film thickness distribution between the two sheets is 2.8% and 3.3%. At the time point of S r ( p rMe4C p ) 2 24 200906836 g, there is almost no difference between the use of the film formation and the use of the characteristics of the end use. [Comparative Example 5] Using S r Γ *

Formation of a film (1 lCp 2 and S by ALD method using S r CP % instead of the same as in the third embodiment: wide CP) 2' divided by 2" 43. = = = It is used for 1.4 and the time of using 90g = "The amount of supply is reduced by _. 〇 〇 8 5 S Γ CP% Depends on the third embodiment and the fifth comparative example, since fp) 2 It is a liquid at the bubble temperature, so it can supply the vapor stably from the beginning to the end of the charge (10)e. The body of the 〇S: Τ Τ =:; = the temperature of the foaming, the evaporation surface area caused by the condensation; :: The key is insufficient, and the film formation original is Sr (the formation of the sr of the PrMe4Cp ALD method (3) j is set by the stencil system to the same conditions as the third embodiment. The sr obtained in the first embodiment is filled in the foaming cylinder (A) and held at 155^^^^200906836 to circulate and foam the argon (A r ) gas 50 sccm while obtaining sr (P r M e 4 C p ) 2 vapor. Further, the cylinder (B) filled with τ i ( 〇ipr ) 4 is maintained at 5 5 χ:, and argon (A r ) gas 2 〇〇S c C m is circulated and foamed At the same time T i (〇ipr ) 洛 =. In addition, the oxidant system makes 〇 2 / N2 = 5 0 0 / 0 . 5 S cc gas into the ozone generator to obtain a density of 1 800 g / m3 C) 'Further, the flushing gas system uses A ^ 2 〇◦ s ◦ c ΙΏ. The pulsation and flushing are performed by pulsing A and B for ten seconds, C pulsing for two seconds, and rinsing for ten seconds to perform the following ALD operation. The s: 〇 formation cycle and the (B pulsation-flush-c pulsation-flush) τ soil ^ 2 formation cycle are used to perform the mouth cycle, and constitute S r 0 / T i〇2 cycle ratio = 1.2, specifically 1 (A pulsation-flush-C pulsation-=washing) 2 cycles, (B pulsation-flushing-c pulsation-flushing) 2 cycles, "A pulsation-flushing- c pulsation-flushing) 2 cycles, (b pulsation-flushing: c pulsation-flushing) 2 cycles, (8 pulsation-flushing-c pulsation-(B-pulse-flush-c-pulse-flush) one of the upper cycles of the sequence is set to - times, and repeating it seven times to form a film of thickness 5 (four) of 丁1〇3. When investigating the formed film composition by XRF method, &amp; =1 · 2 5 [Fifth Embodiment Using Sr (Pr]Vip η , Α τ η, + 0 rr μ e 4 C Ρ ) 2 and forming sr Τ ι 〇 3 film by ALD method (4) film formation to system is the same as that of the third embodiment Condition setting. The s r ( ρ dissolved by the first embodiment is dissolved in a stupid, and is made into 〇 4 mol / 24 P } 2 , 斗 / 1 / 奋 liquid, the viscosity is 4 26 200906836

0 c P ^ = body supply system solution is directed to the turtle that has heated C, and argon (Ar) gas = 〇 gas, and 〇〇〇, /n^., cm as the carrier ifc ^ # 1 η The flow rate is vaporized by the liquid flow meter ~ 抆 surface, and the Sr surface is obtained, (A). Moreover, using a liquid supply system, the amount of enthalpy is increased by (〇ι4ρ^ gas to a gasifier and argon Ur), and the volume flowmeter-surface (four)-surface is vaporized. Second-rate 1 1 ) 4 helium. In addition, the oxidant is obtained by 〇2//N2=5" / 3. 5 s c (four) mixed gas to the ozone generator] 8 = concentration of 〇 3 gas (C), and , flushing gas system using [ ◦ 0 sccm.将该 The pulsation and rinsing are performed by pulsing A and B for two seconds, c pulsing for two seconds, and rinsing for five seconds to perform the following A L D operation.

The Sr〇 formation period using (A pulsation-flushing-c pulsation-flushing) and the formation period of the B-pulse formation using (B-pulse-flush-c-pulse-flush) are performed for a total of 9 9 cycles, and constitute S r〇 /T丨〇2 weeks/month is 1.2. Specifically, 5, (A pulse-flush-c-pulse-flush) 2 cycles, (B-pulse-flush-c-pulse-flush) 2 cycles, (A pulse one Flush a C pulse-flush) 2 cycles, (B pulse-flush-C-pulse-flush) 2 cycles, (A pulse-flush-c pulse-flush) 2 cycles, (B pulse-flush-c-pulse-flush)1 One of the cycles is not repeated once, and it is repeated nine times to form a S r T i 0 3 film having a thickness of 6.4 η ηι. Use the S r i i 〇 3 film, and make the upper and lower electrodes simultaneously into a 27 200906836 heart to make a fire ^ "metal - insulator - metal worry...

Insulator M e t a 1 ) , ^ ^ g 〇 〇 〇〇 When the heat treatment is performed to crystallize S r T 1〇3, the film thickness of the oxide film is 〇 7 nm, and the leakage current when the voltage i v is applied is

, A/Cm2. U [sixth comparative example] s r Cp% was used and the formation of the s r i i 〇 3 film by the ald method (2) was replaced with a SrCp% 0.2 mol/1 toluene solution. The film was formed in the same manner as in the above-mentioned four-part method except for the (J:MrCp) 2 〇.4 mol/1 toluene solution. The use of (A pulsation-rinsing-c pulsation-flushing) si 〇 formation cycle and the use of (B pulsation-flushing-c pulsation-flushing) of the butyl soil formation cycle for a total of 9 9 cycles, and constitutes sr〇 / τ 〇 2 1.2 ' Specifically, (A pulsation - flush - c pulsation 2: 冼) 2 cycles, (B pulsation - flush - c pulsation ~ flush) 2 cycles, (A pulsation - flush - c pulsation - flush 2 cycles, ((4) dynamic-rush, first/pulsation-flush) 2 cycles, (six-pulse-flush 1 pulsation-flushing cycle: (B-pulse-flush-C pulsation-flush) cycle] - times' and repeats it nine times to form a thick

SrTi〇3 film. ...m uses the S r T i〇3 film, and the upper and lower electrodes are simultaneously R u to form a μ ί M structure, and the heat treatment of 6 ◦ 3 〇 3 is crystallized by the heat treatment of 6 ◦ The thickness is 〇. gn claw, the leakage current at voltage IV is 2 · 4χ 1〇-3A/cm2. Compared with the S rTi 〇3 film of the fifth embodiment, although the physical thickness of the s rT 1 〇3 film and the thickness of the oxide film are thick, the leakage current is 28 200906836, which is the fifth implementation. The sr T i〇3 film of the sixth comparative example and the film were formed on the Si substrate at a film thickness of 5 nm, respectively, and the N a content was compared by TXR F (total reflection fluorescent X-ray) analysis, the sixth comparative example. It is twice as large as the fifth embodiment. From this, it can be seen that compared with S r ( P r M e 4 C p ) 2, since there are many impurities such as N a of S 1 C p 2 , electrical characteristics are deteriorated. [Sixth embodiment] The formation of the film forming chamber using S r ( P r M e 4 cp ) 2 and the S r R u 〇 3 film by the ALD method is set to 350 volts to The wafer temperature was set to 3 3 under the conditions of 3 〇 rr, and the same conditions as those in the third embodiment were set. It will be prepared by dissolving in toluene in the 'th. Use liquid to supply the solution to a gasifier that has been heated to 2 Torr, and

The S r (pr μ e 4 C p hurricane / Α 1 ) gas obtained as a carrier gas was used as a carrier gas, and the helium gas was controlled by a liquid flow meter-surface at a flow rate of 0 1 n: Obtain Sr (PrMe'CP) 2 gas (A). Using the liquid limb supply system, the gas of Ru (E t to 1 2 〇 °c is cried, and the crucible has been heated as a carrier gas: and: 〇 = gas 2 〇〇 SCCm meter and batch 4 | one U. The flow rate of 1 g/min is vaporized by the PL surface of the liquid stream, and Ru (E t CP) π pores are obtained at the same time. Further, the oxidant system makes the 〇2/N2 = cm mixture gas to the ozone generation 3 ^ S ° Ο 31 ^ rr ^ ^ + Wang. ° to pass the 1 〇〇g / m3 concentration; (:) 'More' flushing gas system using Ar2 〇〇 sccm. Pulsing and flushing with A, B pulsation - seconds, Pulsation-second, 29 200906836 Flush for two seconds to perform the following ALD operation. The S r 〇 will be used to form the cycle and use (A pulsation-flush-c pulsation-flush). 〇2 formation cycle totals 2 4 〇 cycles, and constitutes sr〇/R u 〇2 cycle ratio =1, specifically, (A pulsation-flush-c pulsation-flush) 2 cycles, (B pulsation-flush one ◦Pulse-flush) One of the two cycles of the series is set to one time, and it is repeated sixty times to form a S r R u 0 3 film having a thickness of 28 nm. [Seventh embodiment Using S r (p r μ e 4 C p) 2 and s r c VD using the method of manufacturing a 〇3 membrane of T i P) 2 red foaming steam, to the chamber C V D.

M e 2 ) 4 vapor is sent to the c V D chamber. The sr (pre 1匚 and S r (p rMe/lCp) 2 vapor obtained by the first embodiment will be filled with argon gas 5 〇 sccm at 1 600 ° C and an internal pressure of about 5 〇 rr rr. R was sent with argon 50 sc: foaming, and T i ( ]\j again, oxygen rolling 1 〇〇 sccm was sent to the cv D chamber.

30 200906836 p ) 2 cylinders are foamed and s r (p r M e 4 c p ) 2 vapor is sent to the C V D chamber. At the same time, the cylinder filled with ru (E tcp) 2 was bubbled with argon gas 5 〇sccm at 30 ° C and an internal pressure of about 7 〇 rr, and the Ru (E t Cp) 2 vapor was sent to the CVD chamber. . When the gas is mixed at the inlet of the C VD chamber and introduced into the 3 1 '1 丁 1 〇 3 (1 〇〇) substrate held at 5 τ 〇r 1, 700 C, S r can be formed at a thickness of 80 nm in thirty minutes. R u Os film. The above description is only a detailed description of the specific embodiments of the present invention, and the present invention is not limited thereto, and is not intended to limit the present invention, and all the scope of the present invention should be In the following claims, the spirit of the claims and the similar changes to the embodiments of the invention are included in the scope of the invention, and any one skilled in the art is within the scope of the invention. Variations or modifications that can be easily conceived are covered by the patents in this case below. BRIEF DESCRIPTION OF THE DRAWINGS The first figure shows the measured spectrum of 2 Η-nm R of the second distillation product of the first embodiment; the second figure shows the vacuum-dried product of the first embodiment! The measured spectrum of H-nm R; the third figure shows the second steamed crane product of the first embodiment! The TG-DTA measurement result chart at atmospheric pressure; the fourth figure shows the TG-DTA measurement result chart of the vacuum drying product of the first embodiment at the atmospheric pressure; the fifth figure shows the second comparison of the first comparative example. The measured spectrum of iH - nm 31 200906836 R of the evaporated product; and the sixth figure shows the results of the TG-DTA measurement of the second distillation product of the first comparative example at 1 atm. [Main component symbol description] /, ", f / k 32

Claims (1)

200906836, the scope of application for patents: 1. A raw material for forming a film containing bismuth, which is 雔 曱 戍 戍 锶). Further, according to the first aspect of the patent application, the raw material for forming a film containing lithium, wherein the content of Na and K is less than 50 ppb: 3 - for forming a film containing Wei The raw material method is obtained by the following procedure to obtain bis(propanthene cyclopentadienyl) hydrazine, that is, to react with sodium tetramethylcyclopentene or propyltetradecyl pentoxide, and to produce double (c) Procedure for removing tetrahydrofuran-addition of tetramethylcyclohexane; a procedure for removing tetrahydro-seven, and extracting toluene by deuterated benzene to remove toluene and drying under reduced pressure; and 氡二ΐ::heat To 10 0~16 〇. ° 'And the process of removing the four mouse after the dissociation and distilling.