Ferroelectricity and thermal retention through in situ hydrogen plasma treatment of doped hafnium oxide
11424271 · 2022-08-23
Assignee
Inventors
- Toshikazu Nishida (Gainesville, FL, US)
- SAEED MOGHADDAM (GAINESVILLE, FL, US)
- Glen H. Walters (Boise, ID, US)
- Aniruddh Shekhawat (Gainesville, FL, US)
Cpc classification
H10B53/00
ELECTRICITY
H01L21/02565
ELECTRICITY
H01L21/022
ELECTRICITY
International classification
H01L21/00
ELECTRICITY
H01L27/12
ELECTRICITY
H01L27/00
ELECTRICITY
H01L21/02
ELECTRICITY
Abstract
Various examples are provided related to hydrogen plasma treatment of hafnium oxide. In one example, a method includes depositing a monolayer of a precursor on a first oxide monolayer; forming a second oxide monolayer by applying an oxygen (O.sub.2) plasma to the monolayer of the precursor; and creating oxygen vacancies in the second oxide monolayer by applying a hydrogen (H.sub.2) plasma to the second oxide monolayer. In another example, a device includes a hafnium oxide (HfO.sub.2) based ferroelectric thin film on a first side of a substrate and an electrode layer disposed on the HfO.sub.2 based ferroelectric thin film opposite the substrate. The HfO.sub.2 film includes a plurality of oxide monolayers including at least one HfO.sub.2 monolayer, each of the plurality of oxide monolayers having oxygen vacancies distributed throughout that oxide monolayer.
Claims
1. A method, comprising: depositing a monolayer of a precursor on a first oxide monolayer; forming a second oxide monolayer by applying an oxygen (O.sub.2) plasma to the monolayer of the precursor; and creating oxygen vacancies in the second oxide monolayer by applying a hydrogen (H.sub.2) plasma to the second oxide monolayer.
2. The method of claim 1, wherein the precursor is a hafnium (Hf) precursor and the second oxide monolayer is a hafnium oxide (HfO.sub.2) monolayer.
3. The method of claim 2, wherein the first oxide monolayer is a zirconium oxide (ZrO.sub.2) monolayer.
4. The method of claim 1, wherein the first oxide monolayer is a hafnium oxide (HfO.sub.2) monolayer.
5. The method of claim 4, wherein the precursor is a zirconium (Zr) precursor and the second oxide monolayer is a zirconium oxide (ZrO.sub.2) monolayer.
6. The method of claim 1, wherein the first oxide monolayer is disposed on a substrate.
7. The method of claim 6, wherein the substrate comprises silicon (Si) or germanium (Ge).
8. The method of claim 6, wherein the substrate comprises a metal layer upon which the first oxide monolayer is deposited.
9. The method of claim 8, wherein the metal layer comprises titanium nitride (TiN), iridium (Ir), ruthenium (Ru), platinum (Pt) or molybdenum (Mo).
10. The method of claim 1, comprising: depositing a monolayer of a second precursor on the second oxide monolayer; and forming a third oxide monolayer by applying an oxygen (O.sub.2) plasma to the monolayer of the second precursor.
11. The method of claim 10, comprising creating oxygen vacancies in the third oxide monolayer by applying a hydrogen (H.sub.2) plasma to the third oxide monolayer.
12. The method of claim 10, wherein the second precursor is a hafnium (Hf) precursor and the third oxide monolayer is a hafnium oxide (HfO.sub.2) monolayer.
13. The method of claim 12, wherein the precursor is a zirconium (Zr) precursor and the second oxide monolayer is a zirconium oxide (ZrO.sub.2) monolayer.
14. A device, comprising: a substrate; a hafnium oxide (HfO.sub.2) based ferroelectric thin film on a first side of the substrate, the HfO.sub.2 based ferroelectric thin film comprising a plurality of oxide monolayers including at least one zirconium oxide (ZrO.sub.2) monolayer disposed adjacent to a plurality of adjacent HfO.sub.2 monolayers, each of the plurality of oxide monolayers individually formed with oxygen vacancies distributed throughout that oxide monolayer; and an electrode layer disposed on the HfO.sub.2 based ferroelectric thin film opposite the substrate.
15. The device of claim 14, wherein the substrate comprises silicon (Si) or germanium (Ge).
16. The device of claim 14, wherein the plurality of oxide monolayers comprises a ZrO.sub.2 monolayer disposed between two HfO.sub.2 monolayers.
17. The device of claim 16, wherein the plurality of oxide monolayers comprises a plurality of alternating HfO.sub.2 and Z.sub.rO2 monolayers, wherein the plurality of oxide monolayers includes a plurality of HfO.sub.2 and a plurality of ZrO.sub.2 monolayers.
18. The device of claim 14, comprising a metal layer disposed between the HfO.sub.2 based ferroelectric thin film and the first side of the substrate.
19. The device of claim 18, wherein the metal layer comprises titanium nitride (TiN), iridium (Ir), ruthenium (Ru), or molybdenum (Mo).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
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DETAILED DESCRIPTION
(7) Disclosed herein are various examples related to hydrogen plasma treatment of hafnium oxide. Reference will now be made in detail to the description of the embodiments as illustrated in the drawings, wherein like reference numbers indicate like parts throughout the several views.
(8) Hafnium oxide based ferroelectric thin films have been explored over the past decade since the discovery that silicon doped hafnium oxide could produce a hysteresis and remanent polarization. Varying the silicon doping has been shown to result in an array of films from ferroelectric to anti-ferroelectric. Other dopants such as Al, Gd, La, Zr, and Y can also produce ferroelectricity in hafnium oxide films. Similarly, in a hafnia-zirconia solid solution, varying the ratio of HfO.sub.2 to ZrO.sub.2 produces a wide range of ferroelectric and anti-ferroelectric films. Aside from dopants alone, ferroelectricity may be affected by a number of factors including deposition temperature, post-metallization annealing, oxidation pulse time during atomic layer depositions (ALD), and the oxygen flow rate during sputter depositions.
(9) Ferroelectric hafnium is highly CMOS compatible, and due to its ultra-thin nature, provides excellent scalability for a wide range of applications. For example, ferroelectric random access memory (FeRAM) can benefit from the advantages offered by HfO.sub.2 based ferroelectric thin films.
(10) The capacitor structure of
(11) Presented in this disclosure is the application of O.sub.2 and sequential O.sub.2, H.sub.2 plasma oxidation methods to control the behavior of the resulting films from anti-ferroelectric to ferroelectric.
(12) For the sequential O.sub.2, H.sub.2 plasma films, O.sub.2 plasma is applied after the precursor pulse and then followed by H.sub.2 plasma as shown in
(13) It has been found that the best performance comes from 1:1 layering of HfO.sub.2 and ZrO.sub.2. In some embodiments, the 1:1 ratio can be maintained but with deposition of thicker HfO.sub.2 or ZrO.sub.2 layers (e.g., 2 Å:2 Å or 5 Å:5 Å). For example, the total film thickness can be in a range from about 3 nm to about 30 nm for a good ferroelectric film. As the layer thicknesses increase, the desired electrical performance will be lost because the device will start to behave as one with two different films instead of a homogeneous mixture. Pure ZrO.sub.2 is anti-ferroelectric above a certain thickness and HfO.sub.2 is weakly ferroelectric.
(14) The process of
(15) Hysteresis results demonstrate the effect of the sequential O.sub.2, H.sub.2 plasma on the remanent polarization (Pr). For film thicknesses of 10, 8, and 6 nm, the sequential O.sub.2, H.sub.2 plasma films have the highest virgin state Pr of 18, 16, and 13 μC/cm.sup.2 compared to 9, 5, and 1.4 μC/cm.sup.2 for H.sub.2O films, and <1 μC/cm.sup.2 for O.sub.2 plasma films at 10 and 8 nm (where the films are anti-ferroelectric) and 0 μC/cm.sup.2 at 6 and 4.5 nm (where the films are paraelectric). Further still, in the virgin state the sequential O.sub.2, H.sub.2 plasma film at 4.5 nm displays anti-ferroelectricity whereas the H.sub.2O and O.sub.2 plasma films are paraelectric.
(16) Endurance tests of the films were carried out via PUND pulses. As with the hysteresis results, the large virgin state polarization is readily apparent for the sequential O.sub.2, H.sub.2 plasma films, whereas the HZO films require wake-up cycling of 10.sup.6 switching cycles to match the switched polarization of 34 μC/cm.sup.2 attained by the sequential O.sub.2, H.sub.2 plasma film at 10 and 8 nm. At 4.5 nm, only the sequential O.sub.2, H.sub.2 plasma film showed a switched polarization, appearing initially anti-ferroelectric but waking up to a switched polarization of 7.6 μC/cm.sup.2 after 10.sup.7 switching cycles.
(17) The use of O.sub.2 and sequential O.sub.2, H.sub.2 plasma during the ALD process offers significant tuning of the hafnium zirconium oxide (HZO) film properties from anti-ferroelectric to ferroelectric. One significant effect of the sequential O.sub.2, H.sub.2 plasma process is the occurrence of the ferroelectric phase after PDA. Without this process, the occurrence of significant ferroelectricity typically requires the PMA step after the capping TiN metallization step. It is theorized that the application of the H.sub.2 plasma during deposition is able to partially reduce the previously deposited oxide, generating oxygen vacancies and enhancing the orthorhombic phase. Among three different oxidizing conditions applied during ALD deposition of 4.5, 6, 8, and 10 nm thick HZO films, the addition of the H.sub.2 plasma after the oxidation treatment increased the virgin state switched polarizations compared to H.sub.2O and O.sub.2 plasma films. The O.sub.2 plasma films were initially anti-ferroelectric and required 10.sup.8 switching cycles to open the hysteresis loop. Additionally, the sequential O.sub.2, H.sub.2 plasma films had the best thickness scalability with the 10, 8, and 6 nm films exhibiting switched polarizations of about 34 μC/cm.sup.2 after 10.sup.6 switching cycles. This addition of H.sub.2 plasma during ALD improves the remanent polarization and thermal retention of the resulting devices over films which have not been treated with hydrogen plasma. Strong thermal retention is important for commercial adoption of ferroelectric hafnium zirconium oxide films for nonvolatile memory device applications.
(18) Experiment
(19) Atomic layer deposition of 1:1 hafnium zirconium oxide films (HZO) was carried out using tetrakis(dimethylamido)hafnium(IV) (TDMAH) and tetrakis(dimethylamido)zirconium(IV) (TDMAZ). Three different oxidizing treatments were utilized: H.sub.2O, O.sub.2 plasma, and sequential O.sub.2, H.sub.2 plasma. For the sequential O.sub.2, H.sub.2 plasma films, O.sub.2 plasma was applied after the precursor pulse followed by H.sub.2 plasma. Using the three oxidizing conditions, 4.5, 6, 8, and 10 nm thick films were grown by employing the tiered deposition method described previously. From ellipsometry measurements of the about 10 nm thick HZO films grown directly on silicon, the growth rate for H.sub.2O oxidized films was determined to be 1 Å per cycle, whereas the growth rate for both O.sub.2 and sequential O.sub.2, H.sub.2 plasma films was slightly lower at 0.8 Å per cycle.
(20) Bottom electrodes of 10 nm thick TiN were fabricated on p+ silicon using tetrakis(dimethylamido)titanium(IV) (TDMAT) and nitrogen plasma. Top electrodes of TiN were similarly deposited, sandwiching the above HZO films to form a metal-ferroelectric-metal (MFM) film stack. MFM capacitors were fabricated by sputtering 50 nm thick platinum which, following lift-off, was used as a hard mask to etch the exposed TiN in H.sub.2O.sub.2 heated to 65° C., creating device areas ranging from 1600 to 14400 pmt. A rapid thermal anneal (RTA) was carried out at 500° C. for 20 s in N.sub.2. Hysteresis and positive-up-negative-down (PUND) tests were carried out with an Agilent 33500B waveform generator and a Tektronix TDS5104B oscilloscope. Hysteresis measurements were taken at 1 and 2 kHz while PUND tests were executed with 1-10-1 μs pulses. Wake-up cycling was performed at 100 kHz with a bipolar square wave.
(21) Test Results
(22) Hysteresis results shown in
(23) Endurance tests of the films were carried out via PUND pulses.
(24) The differences in switched polarization and wake-up between the films can be illustrated by examining the raw voltage responses from the PUND pulses.
(25) Oxygen vacancies play an important role in ferroelectric hafnium oxide from the observed wake-up effect, to charge transport through the film, and stabilization of crystal phases. Indeed, oxygen vacancies, generated by under-pulsing the oxidizing dose such as O.sub.3 or H.sub.2O, can induce ferroelectricity in un-doped hafnium oxide. Similar to under-oxidizing the material during growth, the improved ferroelectricity in the sequential O.sub.2, H.sub.2 plasma films may be attributed to the partial reduction of the deposited oxide via the subsequent H.sub.2 plasma treatment. In an experiment on resistive switching in hafnium oxide, it was shown that hydrogen plasma treatment during the top TiN deposition partially reduced the underlying hafnium oxide layer and generated oxygen vacancies. Further, H.sub.2 plasma can be used in ALD processes for the deposition of single-element materials and, for the case of Al.sub.2O.sub.3 and IrO.sub.2, can reduce the deposited oxide.
(26) The use of O.sub.2 and sequential O.sub.2, H.sub.2 plasma during the ALD process offers significant tuning of the HZO film properties from anti-ferroelectric to ferroelectric. It is theorized that the application of the H.sub.2 plasma during deposition is able to partially reduce the previously deposited oxide, generating oxygen vacancies and enhancing the orthorhombic phase. Among three different oxidizing conditions applied during ALD deposition of 4.5, 6, 8, and 10 nm thick HZO films, the addition of the H.sub.2 plasma after the oxidation treatment increased the virgin state switched polarizations compared to H.sub.2O and O.sub.2 plasma films. The O.sub.2 plasma films were initially anti-ferroelectric and required 10.sup.8 switching cycles to open the hysteresis loop. Additionally, the sequential O.sub.2, H.sub.2 plasma films had the best thickness scalability with the 10, 8, and 6 nm films exhibiting switched polarizations of about 34 μC/cm.sup.2 after 10.sup.6 switching cycles.
(27) Temperature is another challenge facing the integration of hafnium based memories due to the relatively low temperature at which depole and imprint occur. When the sequential O.sub.2, H.sub.2 plasma films are compared to commercially available PZT, the switched positive polarization was found to be favorable. Additional details regarding the methods disclosed herein can be found in U.S. provisional application Ser. No. 62/891,238, filed Aug. 23, 2019, which is hereby incorporated by reference in its entirety.
(28) It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.
(29) The term “substantially” is meant to permit deviations from the descriptive term that don't negatively impact the intended purpose. Descriptive terms are implicitly understood to be modified by the word substantially, even if the term is not explicitly modified by the word substantially.
(30) It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt % to about 5 wt %, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range. The term “about” can include traditional rounding according to significant figures of numerical values. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about y”.