CN103762311B - A kind of ferroelectric memory - Google Patents
A kind of ferroelectric memory Download PDFInfo
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- CN103762311B CN103762311B CN201410038707.1A CN201410038707A CN103762311B CN 103762311 B CN103762311 B CN 103762311B CN 201410038707 A CN201410038707 A CN 201410038707A CN 103762311 B CN103762311 B CN 103762311B
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- 239000010409 thin film Substances 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- -1 aldehyde radical Chemical class 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/20—Organic diodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Semiconductor Memories (AREA)
Abstract
The invention discloses a kind of ferroelectric capacitor of ferroelectric memory, comprising: basalis 1, upper electrode layer 2, top electrode resilient coating 3, ferroelectric thin film layer 4, bottom electrode resilient coating 5, lower electrode layer 6, tack coat 7 and barrier layer 8.Wherein the silacyclohexadiene of multi-substituent is doped in plumbous zirconium ti thin film layer, forms ferroelectric thin film layer 4.
Description
Technical field
The present invention relates to the ferroelectric capacitor for ferroelectric memory, belong to ferroelectric thin-film technology field.
Background technology
The nonvolatile memory of based semiconductor data store and as rotating disk memory substitute in be useful.Find to be used in more and more in computer and consumer devices such as camera, Mp 3 player and PDA based on the memory of Flash EEPROM cells.The cost of Flash EEPROM memory has been reduced to the degree that this memory is used as the substitute of disc driver just in a computer.Because semiconductor disk driver needs significantly lower power, shockproof and typically faster than the conventional disk driver utilized in laptop computer system, so semiconductor disk driver is attractive especially to laptop computer.
Ferroelectric memory is a kind of non-volatile memory of special process, and it adopts the plumbous zirconium titanium PZT material of Prof. Du Yucang to form memory crystalline solid.Ferroelectric memory still can continue to preserve data after a power failure, and writing speed is fast and have the unlimited write life-span, is not easy to write bad.Therefore, with the Nonvolatile memory Technical comparing that flash memory and EEPROM etc. are more early stage, ferroelectric memory has higher writing speed and longer reading-writing life-span.
PZT ferroelectric capacitor, as the main storage medium of ferroelectric memory, has larger fatigue rate and poor leakage current characteristic, and because the ferroelectric thin film crystal property prepared on Pt metal is poor, make the poor performance of PZT ferroelectric capacitor, leakage current is large.Meanwhile, current ferroelectric memory also has a lot of shortcoming.The cost of memory is according to very high, and reading-writing life-span is permanent not, the problems such as easy damage.
Summary of the invention
The present invention mixes organic material in plumbous zirconium titanium (PZT) material, ferroelectric film is made to have following superperformance: to be combined well with electrode, crystal property is good, leakage current is little, material of excellent fatigue characteristics, read or write speed is fast, increases the life-span of ferroelectric memory, and makes ferroelectric memory be not easy to damage.
A ferroelectric capacitor for ferroelectric memory, silicon substrate layer 1, it also comprises upper electrode layer 2, top electrode resilient coating 3, ferroelectric thin film layer 4, bottom electrode resilient coating 5, lower electrode layer 6, tack coat 7 and barrier layer 8.
Wherein the silacyclohexadiene of multi-substituent is doped in plumbous zirconium ti thin film layer, forms ferroelectric thin film layer 4, as the silacyclohexadiene of multi-substituent.
Multiple substituent silacyclohexadiene:
In formula (1), R1, R2 are identical or different, represent alkyl or aryl; R3 represents hydrogen, aldehyde radical, ketone group, ester group, phosphate; R4 represents alkyl, aryl; R5 represents hydrogen, alkyl, thiazolinyl, aryl; R6 represents alkyl, aryl.The straight or branched alkyl of the preferred C1-C6 of above-mentioned alkyl, as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, hexyl etc.
The preferred phenyl of above-mentioned aryl and substituted-phenyl, described substituted benzene such as tolyl, p-methoxyphenyl etc.Above-mentioned ketone group is-COR preferably, and wherein R represents methyl, ethyl, propyl group, phenyl etc.Above-mentioned ester group is-COOR ' preferably, and wherein R ' represents methyl, ethyl, propyl group, phenyl etc.The alkenyl of the preferred C2-C8 of above-mentioned thiazolinyl, such as: vinyl, propenyl, cyclobutenyl, pentenyl etc.
Preferred polysubstituted silacyclohexadiene of the present invention is selected from following compounds Ia ~ If:
Ia：R1＝R2＝Me，R3＝COOMe，R4＝Ph，R5＝H，R6＝Ph；
Ib：R1＝R2＝Ph，R3＝COOMe，R4＝Ph，R5＝H，R6＝Ph；
Ic：R1＝R2＝Me，R3＝COPh，R4＝Ph，R5＝H，R6＝Ph；
Id:R1=R2=Me, R3=COOMe, R4=Ph, R5=(1-propyl group)-1-pentenyl, R6=Ph;
Ie：R1＝R2＝Me，R3＝COOMe，R4＝Bu，R5＝Et，R6＝Bu；
If：R1＝R2＝Ph，R3＝COOMe，R4＝Bu，R5＝Et，R6＝Bu。
Accompanying drawing explanation
Fig. 1 is the structural representation of the ferroelectric capacitor of ferroelectric memory of the present invention.
Embodiment
In order to make the clearer understanding of those skilled in the art technical scheme of the present invention, below in conjunction with accompanying drawing, its embodiment is described.
The ferroelectric capacitor of ferroelectric memory, silicon substrate layer 1, it also comprises upper electrode layer 2, top electrode resilient coating 3, ferroelectric thin film layer 4, bottom electrode resilient coating 5, lower electrode layer 6, tack coat 7 and barrier layer 8.
The present invention mixes organic material in plumbous zirconium titanium (PZT) material, and the illustrated structure of invention is the profile of the ferroelectric capacitor structure of general ferroelectric memory.
The silacyclohexadiene of multi-substituent is doped in plumbous zirconium ti thin film layer, forms ferroelectric thin film layer 4, as the silacyclohexadiene of multi-substituent.
Multiple substituent silacyclohexadiene:
In formula (1), R1, R2 are identical or different, represent alkyl or aryl; R3 represents hydrogen, aldehyde radical, ketone group, ester group, phosphate; R4 represents alkyl, aryl; R5 represents hydrogen, alkyl, thiazolinyl, aryl; R6 represents alkyl, aryl.The straight or branched alkyl of the preferred C1-C6 of above-mentioned alkyl, as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, hexyl etc.The preferred phenyl of above-mentioned aryl and substituted-phenyl, described substituted benzene such as tolyl, p-methoxyphenyl etc.Above-mentioned ketone group is-COR preferably, and wherein R represents methyl, ethyl, propyl group, phenyl etc.Above-mentioned ester group is-COOR ' preferably, and wherein R ' represents methyl, ethyl, propyl group, phenyl etc.The alkenyl of the preferred C2-C8 of above-mentioned thiazolinyl, such as: vinyl, propenyl, cyclobutenyl, pentenyl etc.
Preferred polysubstituted silacyclohexadiene of the present invention is selected from following compounds Ia ~ If:
Ia：R1＝R2＝Me，R3＝COOMe，R4＝Ph，R5＝H，R6＝Ph；
Ib：R1＝R2＝Ph，R3＝COOMe，R4＝Ph，R5＝H，R6＝Ph；
Ic：R1＝R2＝Me，R3＝COPh，R4＝Ph，R5＝H，R6＝Ph；
Id:R1=R2=Me, R3=COOMe, R4=Ph, R5=(1-propyl group)-1-pentenyl, R6=Ph;
Ie：R1＝R2＝Me，R3＝COOMe，R4＝Bu，R5＝Et，R6＝Bu；
If：R1＝R2＝Ph，R3＝COOMe，R4＝Bu，R5＝Et，R6＝Bu。
Below, describe embodiments of the invention in detail, but the present invention is not limited thereto.
According to diagrammatic cross section structure, ferroelectric memory electric capacity is set, basalis 1 is set, together with upper electrode layer 2, top electrode resilient coating 3, ferroelectric thin film layer 4, bottom electrode resilient coating 5, lower electrode layer 6, tack coat 7 and barrier layer 8 are bonded and fixed in turn according to order from top to bottom, barrier layer 8 is bonded and fixed in silicon substrate layer 1.
Wherein polysubstituted silacyclohexadiene, use this area common technology means to be doped in plumbous zirconium ti thin film layer, forming thickness is the thin layer of 290nm to 300nm.
Tack coat 7 can adopt titanium dioxide tack coat, and thickness is 8-10nm; Top electrode resilient coating 3 and bottom electrode resilient coating 5 all adopt colossal magnetoresistance material to make; The thickness of top electrode resilient coating 3 is 70-80nm; The thickness of bottom electrode resilient coating 5 is 15-20nm; Barrier layer 8 is silicon dioxide blocking layer, and thickness is 30-460nm; Upper electrode layer 2 and lower electrode layer 6 are platinum electrode layer, and the thickness of lower electrode layer 6 can be 60-70nm, and the thickness of upper electrode layer 2 is 60-70nm.
Certainly; the present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection range that all should belong to the claim appended by the present invention.
Claims (6)
1. a ferroelectric capacitor for ferroelectric memory, comprising:
Basalis (1), upper electrode layer (2), top electrode resilient coating (3), ferroelectric thin film layer (4), bottom electrode resilient coating (5), lower electrode layer (6), tack coat (7) and barrier layer (8);
Wherein the silacyclohexadiene of multi-substituent is doped in plumbous zirconium ti thin film layer, forms ferroelectric thin film layer (4), multiple substituent silacyclohexadiene:
In formula (1), R
1, R
2identical or different, represent alkyl or aryl; R
3represent hydrogen, aldehyde radical, ketone group, ester group, phosphate; R
4represent alkyl, aryl; R
5represent hydrogen, alkyl, thiazolinyl, aryl; R
6represent alkyl, aryl.
2. ferroelectric capacitor as claimed in claim 1, it is characterized in that, above-mentioned alkyl is selected from the straight or branched alkyl of C1-C6.
3. ferroelectric capacitor as claimed in claim 2, it is characterized in that, the straight or branched alkyl of described C1-C6 is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, amyl group, hexyl.
4. ferroelectric capacitor as claimed in claim 1, it is characterized in that, above-mentioned aryl is selected from phenyl or substituted-phenyl; Above-mentioned ketone group is selected from-COR, and wherein R represents methyl, ethyl, propyl group, phenyl; Above-mentioned ester group is selected from-COOR', and wherein R' represents methyl, ethyl, propyl group, phenyl; Above-mentioned thiazolinyl is selected from the alkenyl of C2-C8;
Multiple substituent silacyclohexadiene is selected from following compounds Ia ~ If:
Ia：R
1＝R
2＝Me，R
3＝COOMe，R
4＝Ph，R
5＝H，R
6＝Ph；
Ib：R
1＝R
2＝Ph，R
3＝COOMe，R
4＝Ph，R
5＝H，R
6＝Ph；
Ic：R
1＝R
2＝Me，R
3＝COPh，R
4＝Ph，R
5＝H，R
6＝Ph；
Id:R
1=R
2=Me, R
3=COOMe, R
4=Ph, R
5=(1-propyl group)-1-pentenyl, R
6=Ph;
Ie：R
1＝R
2＝Me，R
3＝COOMe，R
4＝Bu，R
5＝Et，R
6＝Bu；
If：R
1＝R
2＝Ph，R
3＝COOMe，R
4＝Bu，R
5＝Et，R
6＝Bu。
5. ferroelectric capacitor as claimed in claim 4, it is characterized in that, described substituted-phenyl is tolyl, p-methoxyphenyl.
6. ferroelectric capacitor as claimed in claim 4, it is characterized in that, the alkenyl of described C2-C8 is vinyl, propenyl, cyclobutenyl, pentenyl.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410038707.1A CN103762311B (en) | 2014-01-26 | 2014-01-26 | A kind of ferroelectric memory |
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|---|---|---|---|
| CN201410038707.1A CN103762311B (en) | 2014-01-26 | 2014-01-26 | A kind of ferroelectric memory |
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| CN103762311B true CN103762311B (en) | 2016-01-13 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284845A (en) * | 2007-04-10 | 2008-10-15 | 北京大学 | Polysubstituted silacyclohexadiene and synthetic method thereof |
| CN102790091A (en) * | 2009-10-20 | 2012-11-21 | 中芯国际集成电路制造(上海)有限公司 | Green transistor, nanometer silicon FeRAM and driving method thereof |
| CN102964123A (en) * | 2012-12-12 | 2013-03-13 | 中国科学院上海硅酸盐研究所 | Samarium-oxide-doped modified lead zirconate titanate ferroelectric ceramic and preparation method thereof |
| CN103360062A (en) * | 2012-03-30 | 2013-10-23 | 三菱综合材料株式会社 | Ferroelectric thin film-forming sol-gel solution and ferroelectric thin film forming method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0220264D0 (en) * | 2002-08-31 | 2002-10-09 | Univ Cranfield | Improvements to oxide films |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284845A (en) * | 2007-04-10 | 2008-10-15 | 北京大学 | Polysubstituted silacyclohexadiene and synthetic method thereof |
| CN102790091A (en) * | 2009-10-20 | 2012-11-21 | 中芯国际集成电路制造(上海)有限公司 | Green transistor, nanometer silicon FeRAM and driving method thereof |
| CN103360062A (en) * | 2012-03-30 | 2013-10-23 | 三菱综合材料株式会社 | Ferroelectric thin film-forming sol-gel solution and ferroelectric thin film forming method |
| CN102964123A (en) * | 2012-12-12 | 2013-03-13 | 中国科学院上海硅酸盐研究所 | Samarium-oxide-doped modified lead zirconate titanate ferroelectric ceramic and preparation method thereof |
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