CN1238575C - Method of building crystal to grow lead zirconate titanate film - Google Patents
Method of building crystal to grow lead zirconate titanate film Download PDFInfo
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- CN1238575C CN1238575C CN 01136690 CN01136690A CN1238575C CN 1238575 C CN1238575 C CN 1238575C CN 01136690 CN01136690 CN 01136690 CN 01136690 A CN01136690 A CN 01136690A CN 1238575 C CN1238575 C CN 1238575C
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Abstract
The present invention relates to a method for superposing crystals to grow a lead zirconate titanate film. The present invention is characterized in that a layer of nickel lanthana film is grown on a substrate by superposing crystals in an immediate mode, the crystal form of the nickel lanthana film is the same as a needed lead zirconate titanate film, and crystal parameter is approximate to that of the needed lead zirconate titanate film; then, the nickel lanthana thin film is grown on the lead zirconate titanate film by superposing the crystals in the immediate mode in the temperature of 350 DEG C to 500 DEG C.
Description
Technical field
The invention relates to a kind of manufacture method of high dielectric constant film, and particularly relevant for a kind of building crystal to grow lead zirconate titanate (Lead Zirconate Titanate, PbZr
xTi
1-xO
3, the PZT) method of film.
Background technology
Pb-based lanthanumdoped zirconate titanates is a kind of polyfunctional material, it can be used as high dielectric constant material (High-K Material), ferroelectric material (Ferroelectric Material), piezoelectric (Piezoelectric Material) or burnt electric material (Pyroelectric Material), below with brief introduction in regular turn.
One is because PZT thin film has high-k (Dielectric Constant), so can be applicable to the making processes of advanced DRAM (Dynamic Random Access Memory) (DRAM).This is that the size of storage unit (Memory Cell) is constantly dwindled because the integrated level (Integration) of DRAM (Dynamic Random Access Memory) (DRAM) constantly increases, so it is also more and more little to be used for the area of electrical condenser of storage data.Therefore, in order to keep the capacitance of electrical condenser, signal/noise ratio (Signal to Noise Ratio, S/N Ratio) when keeping access data, following trend is to use the material of the high dielectric constant material of Pb-based lanthanumdoped zirconate titanates and so on as dielectric layer in the electrical condenser.
Its two because PZT thin film has very strong spontaneous polarization phenomena (SpontaneousPolarization), promptly after extra electric field disappears, still have the remnant polarization value (P of forward or negative sense
r +Or P
r -, P wherein
rAbbreviation for Residual Polarization), thus can be used as a kind of non-voltile memory (Non-Volatile Memory, NVM), be called Ferroelectric Random Access Memory (Ferroelectric Random Access Memory, FeRAM).Because FeRAM have low read-write voltage and read or write speed faster (＜＜100ns), and its making processes step is less, so can replace present the most frequently used flash memory (Flash Memory).
Its three because PZT thin film has high piezoelectric constant (Piezoelectric Constant), so can produce the potential difference that is enough to for detecting behind its pressurized.Therefore, pzt thin film is applied in the various piezo-electric devices widely, for example is transmitter (sensors), the stopper (actuators) of pressure sensor or vibration, or voltage generator (voltage generators) etc.
Its four because PZT thin film has high burnt electric constant (Pyroelectric Constant), so it when being subjected to infrared ray radiation, can produce the potential difference that is enough to for detecting because of absorbing the heat that infrared rays produces.Therefore pzt thin film can be applicable in infrared sensor (Infrared Sensor) or the thermometer.
Though PZT thin film has so multi-functional, on using, the too high problem of formation temperature is often arranged, especially for the semiconductor fabrication process of PZT thin film as capacitor dielectric.The PZT thin film making processes that United States Patent (USP) case US 5589284 proposes is to form one deck crystal seed layer (seed layer) earlier on the lower electrode of electrical condenser, and its material is ruthenic acid strontium (strontium ruthenate, SrRuO
3), ruthenic acid barium (barium ruthenate, BaRuO
3), or iridium acid calcium (calcium iridiate, CaIrO
3) or the like.Then in about 150 ℃, on crystal seed layer, deposit one deck pzt thin film,, make pzt thin film have the Perovskite crystal formation (roughly being column) of required high-k again in carrying out tempering (annealing) more than 500 ℃.
In addition, the method that US 5817170 is carried also is to form crystal seed layer earlier on lower electrode, and its material is lead titanate (PbTiO
3).Then on crystal seed layer, deposit one deck pzt thin film at a lower temperature, and between 550 ℃ to 650 ℃, carry out tempering.In addition, the method for US 5998236 is to form load lanthanium titanate ((Pb, La) TiO on lower electrode
3, PLT) film deposits pzt thin film more thereon, carries out tempering then between 525 ℃ to 550 ℃.
Yet,,, continue metal interconnect (Metal Interconnection) making processes thereafter again so must make pzt thin film earlier because known each method all need carried out tempering more than 500 ℃.So can produce some problems, the board of first making dielectric layer and metal level is subject to the pollution of pzt thin film; It two is the plasma body that uses in metal interconnect making processes and the hydrogen of generation, and ferroelectric condenser is damaged.
Summary of the invention
Therefore, purpose of the present invention promptly is the method that proposes a kind of building crystal to grow lead zirconate titanate film, and it can form at a lower temperature has required crystal formation and electrical PZT thin film, the problem that produces to avoid Yin Gaowen in the above-mentioned known method.
The method steps of building crystal to grow lead zirconate titanate film of the present invention is as follows: at first the mode with coordination (in-situ) generates one deck lanthanum trioxide nickel (lanthanum nickel oxide, LaNO in substrate
3, LNO) film, its crystal formation is identical with PZT thin film, and lattice parameter (cellparameters) is close with PZT thin film.Then in the mode of coordination, and between 350 ℃～500 ℃, direct building crystal to grow lead zirconate titanate film film on lanthanum trioxide nickel film.The mode of so-called coordination is meant that pzt thin film grows up to required crystal formation when being deposited on the lanthanum trioxide nickel film simultaneously herein, and not like as the known method prior to lower temperature deposit PZT, carry out the pyritous tempering step again.
As mentioned above, because forming the temperature of pzt thin film in the method for the present invention can be far below known, manufacture electrical condenser again and can manufacture the metal interconnect earlier, so avoided the pollution that lower electrode is easy and pzt thin film reacts, board is subject to pzt thin film, and electrical condenser is subject to the problem of plasma collapse.This manufacture earlier the metal interconnect manufacture again the method spy of electrical condenser be called electrical condenser on interconnect making processes (Capacitor Over Interconnect, COI).In addition, because it is lower to form the temperature of pzt thin film in the method for the present invention, so also can be applicable in the making processes of the making processes of piezo-electric device or burnt electric installation, it can be avoided, and metal is online to be subjected to pyritous destruction.
Description of drawings
Fig. 1 is in the embodiments of the invention, the making processes of electrical condenser and PZT thin film wherein;
Fig. 2 is in the embodiments of the invention, shows the lanthanum trioxide nickel film of (TEM) gained and the sectional view of PZT thin film with the penetration electricity;
Fig. 3 A and Fig. 3 B are respectively in the embodiments of the invention, and at 350 ℃ of vertical views with the PZT thin film of 450 ° of following gained, it is got by TEM;
Fig. 4 is in the embodiments of the invention, at the X-ray diffraction spectrum of 325 ℃～450 ℃ pzt thin films that form down; And
Fig. 5 A, Fig. 5 B and Fig. 5 C are respectively in the embodiments of the invention, at 375 ℃, 400 ℃ electro-viscous effect (Ferroelectric Hysteresis) curves with 450 ℃ of pzt thin films that form down.
Description of reference numerals:
100: dielectric layer (Dielectric Layer)
110: the superiors' metal interconnect (Metal Interconnection)
120: dielectric layer (Dielectric Layer)
130: barrier layer (barrier Layer)
140: lanthanum trioxide nickel film/lower electrode (LNO film/Bottom Electrode)
150: PZT thin film (PZT film)
160: top electrode (Top Electrode)
Embodiment
Be that making processes with electrical condenser and wherein PZT thin film is example in the present embodiment, wherein lower electrode and PZT thin film are that the method for being carried with the present invention forms.
Please refer to Fig. 1, dielectric layer 100 at first is provided, it is cmos component and other metal level down, and be formed with the metal interconnect structure 110 and a dielectric layer 120 of the superiors on it, wherein the material of dielectric layer 120 is preferably the formed silicon oxide of plasma enhanced chemical vapor deposition method (PECVD).The reason that can manufacture metal interconnect structure 110 herein earlier as previously mentioned, be since PZT thin film formation temperature of the present invention low due to.
Please continue with reference to Fig. 1, then deposit one deck barrier layer 130 on dielectric layer 120, its material for example is titanium nitride (TiN), titanium tungsten nitride (TiWN), TiAlN (TiAlN), or tantalum nitride (TaN).Then in the mode of coordination, about 350 ℃ on barrier layer 130 sputter growth lanthanum trioxide nickel (LNO) layer 140, it is as lower electrode, and the La in this lanthanum trioxide nickel dam 140 and the mol ratio of Ni are about 1: 1.3.
Please continue with reference to Fig. 1, follow the mode of coordination, sputter is also built crystalline substance simultaneously on lanthanum trioxide nickel dam 140 under 350 ℃～450 ℃, and with growth pzt thin film 150, be straight argon this moment in the system, and can not contain oxygen, in order to avoid reduce the quality of pzt thin film; In addition, the composition of sputter palladium is Pb
yZr
xTi
1-xO
3(y 〉=1).Next on pzt thin film 150, form top electrode 160, its material for example be lanthanum trioxide nickel (LNO), platinum (platinum, Pt), iridium dioxide (iridiumdioxide, IrO
2), ruthenium dioxide (RuO
2), iridium (iridium, Ir), or ruthenium (ruthenium, Ru).
Experimental result
Please refer to Fig. 2, in embodiments of the invention, show the lanthanum trioxide nickel film 140 of (TEM) gained and the sectional view of PZT thin film 150 with the penetration electricity, wherein lanthanum trioxide nickel film 140 is to form under 350 ℃, and PZT thin film 150 is to form under 400 ℃.As shown in Figure 2, PZT thin film 150 is to grow up to making progress along the lattice position of lanthanum trioxide nickel (LNO) film 140, and as seen it is a building crystal to grow.
Fig. 3 A and Fig. 3 B are respectively in the embodiments of the invention, and at 350 ℃ of orthographic plans with the PZT thin film of 450 ° of following gained, it is got by TEM.By Fig. 3 A and Fig. 3 B as seen, the crystallinity of the PZT thin film of 450 ° of following gained is better than 350 ° of following gained.
Fig. 4 is in the embodiments of the invention, and at the X-ray diffraction spectrums of 325 ℃～450 ℃ pzt thin films that form down, this pzt thin film all forms with sputtering way in the argon gas (Ar) of 5mTorr, and the power that is provided is 50W, and employed sputter palladium consist of Pb
1.1Zr
0.53Ti
0.47O
3As shown in Figure 4, formation temperature heal PZT when high the diffraction peak more obviously, the Perovskite crystalline content of expression pzt thin film increases with temperature.Moreover as shown in Figure 4, the diffraction peak of obviously visible PZT (100) and (200) lattice direction is reduced to 350 ℃ even represent the formation temperature of pzt thin film of the present invention in the time of 350 ℃, still can obtain neat crystalline network.In addition, analyze the X-ray diffraction spectrum of pzt thin film after, learn that also a value in the lattice parameter of pzt thin film is 4.036 , the c value is 4.146 ; And a value in the lattice parameter of LNO film is 4.05 , and the c value is 4.09 .Because the lattice parameter of pzt thin film and LNO film is close, so the present invention can at lower temperature deposit pzt thin film, and make it have required crystal formation in the mode of coordination simultaneously.
Fig. 5 A, Fig. 5 B and Fig. 5 C are respectively in the embodiments of the invention, answer (Ferroelectric Hysteresis) curve at 375 ℃, the 400 ℃ ferroelectric residual effects with 450 ℃ of pzt thin films that form down, wherein electric field is that 0 o'clock the forward remnant polarization value and the difference of negative sense remnant polarization value are denoted as 2P
r, and the power-on and power-off voltage across poles 5V and-test result when changing between 5V points out with arrow.Shown in Fig. 5 A, Fig. 5 B and Fig. 5 C, when temperature heals when high, voltage 5V and-2P under the situation that changes between the 5V
rValue is promptly bigger.This 2P
rValue is very important for FeRAM, because the general practice makes the ferroelectric membranc in the electrical condenser have the remnant polarization value of negative sense depositing data value " 1 " in FeRAM the time; And be to make ferroelectric membranc have the remnant polarization value of forward when depositing " 0 " in.Therefore, the difference of negative sense remnant polarization value and forward remnant polarization value is bigger, and " 0 " is promptly bigger with the difference of the read output signal (Readout Signal) of " 1 ", and " 0 " is then little with the erroneous judgement chance of " 1 ".
Above-mentioned pzt thin film is to form with sputtering way in the argon gas (Ar) in 5mTorr, yet, between the pressure range of argon gas in the practical application can be for 1mTorr to 50mTorr, even adjust the size of argon pressure according to the area of target.
In addition, lanthanum trioxide nickel (LNO) layer that is positioned at pzt thin film below in the above-described embodiments is that mode with coordination grows up to the required crystal formation of PZT, i.e. Perovskite type in 350 ℃ of crystalline substances of heap of stone.Yet in the making processes of reality, lanthanum trioxide nickel (LNO) layer grows up to the required crystal formation of PZT only to be needed can grow up to more than 350 ℃.Therefore, cooperate cryogenic demand, lanthanum trioxide nickel of the present invention (LNO) layer also can grow up to required crystal formation by coordination crystalline substance of heap of stone between 350 ℃ to 500 ℃.
As mentioned above, can be low to moderate 350 ℃ owing to form the temperature of pzt thin film in the method for the present invention, its value is far below known, and lanthanum trioxide nickel (LNO) layer that is positioned at the pzt thin film below also can grow up to the required crystal formation of PZT with the mode of coordination crystalline substance of heap of stone between 350 ℃ to 500 ℃, it is the Perovskite type, so method of the present invention can be manufactured the metal interconnect earlier and manufacture electrical condenser again, and avoided the pollution that lower electrode is easy and pzt thin film reacts, board is subject to pzt thin film, and electrical condenser is subject to the problem of plasma collapse.In addition, because it is lower to form the temperature of pzt thin film in the method for the present invention, so also can be applicable in the making processes of the making processes of piezo-electric device or burnt electric installation, it can avoid substrate to be subjected to pyritous destruction.
Though the present invention with embodiment explanation as above; right its is not in order to qualification the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is when being as the criterion with claims.
Claims (18)
1. the method for a building crystal to grow lead zirconate titanate film is characterized by: comprise the following steps:
One substrate is provided;
In the mode of coordination, use sputtering method building crystal to grow one lanthanum trioxide nickel film in this substrate; And
In the mode of coordination, and under 350 ℃～500 ℃ temperature, use sputtering method building crystal to grow one PZT thin film on this lanthanum trioxide nickel film.
2. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1, it is characterized by: the temperature of this PZT thin film of growing up is between 350 ℃ to 450 ℃.
3. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1, it is characterized by: the temperature of this lanthanum trioxide nickel film of growing up is between 350 ℃ to 500 ℃.
4. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: when using sputtering method with this PZT thin film of building crystal to grow in this substrate, be to use to consist of Pb
yZr
xTi
1-xO
3The one sputter palladium of (y 〉=1).
5. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: be to be in the environment of argon gas when growing up this PZT thin film.
6. the method for building crystal to grow lead zirconate titanate film as claimed in claim 5, it is characterized by: when growing up this PZT thin film, the pressure of argon gas is 1mTorr to 50mTorr.
7. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: be to be applied in the making processes of a DRAM (Dynamic Random Access Memory).
8. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: be to be applied in the making processes of a Ferroelectric Random Access Memory.
9. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: be to be applied in the making processes of a piezo-electric device.
10. the method for building crystal to grow lead zirconate titanate film as claimed in claim 1 is characterized by: be to be applied in the making processes of a burnt electric installation.
11. the manufacture method of an electrical condenser is characterized by: comprise the following steps:
One substrate is provided;
Deposition one barrier layer in this substrate;
In the mode of coordination, use sputtering method building crystal to grow one lanthanum trioxide nickel film on this barrier layer, with a lower electrode as this electrical condenser; And
In the mode of coordination, and under 350 ℃～500 ℃ temperature, use sputtering method building crystal to grow one PZT thin film on this lanthanum trioxide nickel film; And
On this PZT thin film, form a top electrode.
12. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: be formed with a metal interconnect structure and the metal intermetallic dielectric layer on it in this substrate, and this barrier layer is formed on this metal intermetallic dielectric layer.
13. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: the material of this barrier layer is selected from by titanium nitride, titanium tungsten nitride, TiAlN, and the group of tantalum nitride composition.
14. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: the material of this top electrode is selected from by lanthanum trioxide nickel, platinum, iridium dioxide, ruthenium dioxide, iridium, and the group of ruthenium composition.
15. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: the temperature of this PZT thin film of growing up is between 350 ℃ to 450 ℃.
16. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: the temperature of this lanthanum trioxide nickel film of growing up is between 350 ℃ to 500 ℃.
17. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: when using sputtering method, use to consist of Pb with this PZT thin film of building crystal to grow in this substrate
yZr
xTi
1-xO
3The one sputter palladium of (y 〉=1).
18. the manufacture method of electrical condenser as claimed in claim 11 is characterized by: when growing up this PZT thin film, be in the environment of argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136690 CN1238575C (en) | 2001-10-26 | 2001-10-26 | Method of building crystal to grow lead zirconate titanate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01136690 CN1238575C (en) | 2001-10-26 | 2001-10-26 | Method of building crystal to grow lead zirconate titanate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1414149A CN1414149A (en) | 2003-04-30 |
| CN1238575C true CN1238575C (en) | 2006-01-25 |
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ID=4673832
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01136690 Expired - Fee Related CN1238575C (en) | 2001-10-26 | 2001-10-26 | Method of building crystal to grow lead zirconate titanate film |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200127B (en) * | 2006-12-15 | 2011-04-20 | 中国科学院合肥物质科学研究院 | Lanthanum zirconic acid/yttrium titanate film material and method for making same |
| JP6457396B2 (en) | 2012-11-30 | 2019-01-23 | クエスト インテグレーテッド， エルエルシー | Lead zirconate titanate single crystal growth method |
| CN116553634B (en) * | 2023-07-07 | 2023-09-05 | 苏州擎动动力科技有限公司 | Ca (calcium) 2 IrO 4 Nanorod and preparation method and application thereof |
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2001
- 2001-10-26 CN CN 01136690 patent/CN1238575C/en not_active Expired - Fee Related
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