See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/316713734

18x36x1.5 inch sapphire panels for visible and infrared windows

Conference Paper · May 2017

DOI: 10.1117/12.2269465

CITATIONS READS
6 698

2 authors, including:

Matthew Montgomery
Rubicon Technology
3 PUBLICATIONS 10 CITATIONS

SEE PROFILE

All content following this page was uploaded by Matthew Montgomery on 01 November 2018.

The user has requested enhancement of the downloaded file.

 18 x 36 x 1.5 inch sapphire panels for visible and infrared windows
Matthew Montgomery, Clark Blockburger
Rubicon Technology, Inc., 900 E. Green St. Unit A, Bensenville, IL USA 60106.
4 May 2017

ABSTRACT

158 kg sapphire single crystals were grown by horizontal directional solidification method. Bubble-free panels with usable
rectangular dimensions of 457 mm x 914 mm x 38 mm (18 x 36 x 1.5 inches) can be cut from the crystals. These are the
largest-area sapphire panels ever produced by any technique. Bubble-free sections of the crystal 300 mm x 457 mm and
up to 60 mm thick (12 x 18 x 2.36 inches) can also be produced. Growths were performed with graphite heating elements
under a controlled atmosphere with automated power control. Results of transmission measurements performed on 5 mm
thick samples are presented and the transmission is similar to sapphire grown by other techniques.

Keywords: sapphire, crystal growth, horizontal directional solidification method, EFG, HDSM, horizontal Bridgman, IR
windows, transmission, single crystal, aluminum oxide, Al2O3, windows, boule, plate, panel, optic, horizontal
directional crystallization, Bagdasarov, HDC, horizontally oriented crystallization, HOC, edge-defined film-fed growth.

1. INTRODUCTION

Singe crystal sapphire (Al2O3) windows excel in challenging conditions. Sapphire’s mechanical hardness, optical
transparency, and chemical inertness make it attractive for uses from semiconductor manufacturing to the battlefield.
Large-area sapphire windows are desirable for such applications. Commercially grown Kyropoulos (KY) and heat
exchanger method (HEM) sapphire boules have reached 300 kg and over 450 mm diameter in the last half-decade, driven
by economies of scale and demand for sapphire substrates for the LED (light emitting diode) industry.1,2 Additionally,
edge-defined film-fed growth (EFG) sapphire is commercially available in plates up to 304 mm x 508 mm.3 However,
larger sapphire windows are desirable for military applications (e.g. 1 meter by 1 meter). Both boule-growth techniques
(like KY and HEM) and EFG face substantial challenges scaling up to those dimensions. A cylindrical boule (with diameter
of 1.4 m and height of 1.4 m) yielding a 1 m x 1 m rectangular window would weigh almost 9000 kg! On the other hand,
EFG and the horizontal directional solidification method (HDSM) allow growth of sapphire in rectangular plates where
the length and width are much greater than the thickness. For producing meter-class windows, this is clearly an advantage
over cylindrical boules. EFG is generally limited to maximum as-grown thicknesses of around 20 mm.4

Using a custom-built HDSM furnace, we have recently grown the largest-area sapphire plates ever produced by any
technique. The sapphire single crystals are 158 kg as-grown, and as-cut have usable rectangular dimensions of 457 mm x
914 mm x 38 mm (18 x 36 x 1.5 inches). They have transmission similar to crystals grown via conventional methods in
the visible and infrared portions of the spectrum. Their mechanical hardness is also comparable.

2. DESCRIPTION OF THE TECHNIQUE

Khachik Bagdasarov developed the HDSM technique starting in the 1960s.5 It is a variation on the horizontal Bridgman
technique. The melt is contained in a molybdenum crucible with a flat bottom and vertical side-walls. The molten zone is
smaller than the total length of the crucible, and the crucible is transported horizontally through the stationary melt-heating
zone, crystallizing as it exits the melt-heating zone.

1
We have previously grown HDSM crystals up to 350 x 940 x 38 mm in vacuum with a tungsten heating element.1 These
crystals could yield a panel with usable dimensions of up to 350 x 508 x 29 mm. To increase the size of the crystals it was
necessary to add afterheating (outside the melt-heating zone) to minimize thermal gradients which can crack the crystals
as they are being grown. The afterheating zone is kept at a temperature over 1850 °C, above the brittle-to-plastic transition
for sapphire. Tungsten heating elements lose strength and are prone to warp at the temperatures required for sapphire
growth (Tm=2050 °C) which makes maintaining temperature uniformity across the crystal growth interface challenging.
We have implemented graphite heating elements for both the melt-heating zone and the afterheating zone. The graphite
elements have several advantages: they are more rigid at high temperatures which improves the uniformity of the
temperature gradient at the growth interface, and improves the repeatability of the process from run-to-run and within one
run; they are significantly less expensive than tungsten elements; and they are more easily handled due to their lower
weight. Graphite heating elements also have disadvantages for sapphire growth. The vapor pressure of graphite becomes
appreciable above 2200 °C, meaning the graphite heating elements quickly degrade if the growth is performed under
vacuum. Work by another group reported that due to microparticles of Al2O3 sub-oxides, visible transmission was
approximately five percentage points lower when HDSM crystals were grown in argon atmosphere at ambient pressure
than when crystals were grown in vacuum.6 Good transmission was achieved at pressures of 0.1 to 0.3 torr, with a
corresponding reduction in microparticle count.7 Graphite is an efficient getter of oxygen, which leads to a highly reducing
atmosphere in the hot-zone. This in turn leads to oxygen deficient non-stoichiometric melt and results in sub-oxide alumina
microparticles in the grown crystal. Our crystals are grown in a controlled atmosphere at ambient pressure. To keep the
sapphire completely thermodynamically stable, a partial pressure of oxygen must be present in the growth atmosphere
greater than approximately 0.1 torr. Thermodynamic incompatibilities between the graphite, the aluminum oxide, and the
atmosphere require trade-offs to be made, as the graphite hot-zone components degrade when the partial pressure of oxygen
is high enough to stabilize the sapphire.8

The furnace power is automatically controlled during the growth by a system based on PID control with feed-forward
recipes. A camera captures an image of the solid-liquid interface, which is then fed to a PC. The image is processed to
determine the position of the solid-liquid interface, which is used to modulate the heating element power. For a constant
pulling speed, if the position of the solid-liquid interface is perfectly stationary in the field of view, then the rate of
crystallization will exactly equal the pulling speed. Using this automated system results in controlled crystal growth with
the growth rate stable +/-10% throughout the process with minimal operator intervention.

3. RESULTS AND DISCUSSION

3.1 Fabrication of large panels

The as-grown sapphire slabs are 1450 mm long, 465 mm wide, and 68 mm thick, and weigh 158 kg. Multiple crack-free,
grain boundary-free crystals have been grown. All crystals of this size grown to date have had the a-plane, (112� 0) as the
major face, and the long edges c-plane (0001), with the growth direction parallel to m-direction <101� 0>. One such crystal
is shown in Figure 1. Characteristically, the crystals have relatively large bubbles in the portion of the crystal close to the
major face of the molybdenum crucible (i.e. the bottom of the crystal thickness) (Figure 2). Crystals grown early in the
project’s development had bubbles exceeding 10 mm diameter in the same region, but were bubble-free for the top 38 mm
of the thickness. By adjusting the hot-zone configuration and growth recipes, the bubbles have been eliminated in the first
third of the growth (right side of Figure 1), and reduced in size to <1 mm diameter in the remaining two thirds (left side
of Figure 1). Continued optimization is underway to eliminate the bubbles entirely. The minimum bubble-free thickness
over a 914 mm length varies from 28 to 38 mm depending on the crystal. This can yield a 457 x 914 mm window up to 38
mm thick. The as-grown crystal can be sliced into multiple thinner panes using a large wire saw. Panels as thin as 6 mm
have been fabricated. Figure 3 shows a 457 x 914 x 29 mm ground blank. Polished windows 356 x 408 x 20 mm and 432
x 635 x 20 mm have been fabricated and are shown in Figure 4. All of these fabricated blanks and windows are grain
boundary-free and bubble-free under visible light inspection. Thicker bubble-free parts up to 300 x 457 x 60 mm are
possible from the first one third of the crystal.

2
Figure 1. 158 kg sapphire slab grown by horizontal directional solidification method (HDSM). The seed is on the right side of the
image, covered by cloth. The largest face is the a-plane. Meter stick in foreground.

Figure 2. Schematic side view of the crystal in Figure 1 showing usable volume. Gray shaded region contains bubbles. Dimensions
in millimeters.

Figure 3. Sapphire panel cut from a crystal similar to Figure 1. The dimensions of the as-cut panel are 457 x 914 x 30 mm. Meter
stick in foreground.

3
 Figure 4. Left: Polished sapphire window: 356 x 508 x 20 mm. The measuring tape is inch ruled. 0.25-inch grid paper behind
window. Right: Polished sapphire window 432 x 635 x 22 mm (with meter stick).

3.2 Crystal growth and material properties

Growth runs performed without sufficient oxygen partial pressure resulted in discolored crystals with a brown or pink
color, and build up of aluminum carbide deposits that could block the view of the crystal-melt interface. We infer the
coloration was caused by anionic vacancies in the crystal lattice due to growth in an oxygen-deficient atmosphere.
Annealing a brown crystal in air at 1600 °C for 12 hours greatly reduced coloration (Figure 5).

3 inches

Figure 5. This portion of a sapphire crystal was grown in a highly reducing atmosphere. The brown color is evidence of anionic
vacancies in the crystal lattice. The section inside the dashed line was annealed in air at 1600 °C for 12 hours.

Manipulating the growth atmosphere to raise the partial pressure of oxygen allowed colorless crystals to be grown at
ambient pressure, with near-elimination of deposits within the hot-zone. The growth atmosphere is still somewhat reducing
however, which leads to sub-oxide alumina microparticles in the crystals. This results in a reduced transmission compared
to KY crystals grown in vacuum with all metal hot-zones (especially below 300 nm), but similar transmission to EFG
crystals and HEM crystals grown in graphite hot-zones. This makes the material less suitable for ultraviolet optical

4
applications and high-intensity lasers than KY sapphire, but suitable for optical imaging applications in the visible and
infrared. Transmission plots are shown in Figures 6 and 7. The transmission is significantly better than other reported
HDSM crystals grown at ambient pressure,6 and similar to HDSM crystals grown at 0.1 – 0.3 torr.7 The Knoop hardness
for an a-plane sample is 2100 kg/mm2, which compares favorably with previously published values.

Figure 6. Transmission curve for a-plane sapphire sample 5.08 mm thick with 60/40 scratch/dig polished surface.

Figure 7. Transmission curve for a-plane sapphire sample 5.08 mm thick with 60/40 scratch/dig polished surface.

5
 4. CONCLUSION

Using the horizontal directional solidifcation method (HDSM), we have grown the largest-area sapphire crystals ever
reported. The optical quality is comparable to EFG and HEM sapphire material in the visible and infrared. Material
availability at these sizes will allow the use of sapphire windows in large-area applications including visible and infrared
optics. While the windows grown here were grown with the major face in the a-plane to facilitate comparison to previous
work and to act as a drop-in replacement for EFG-grown sapphire, HDSM is also amenable to growth of c-plane windows.6
By constructing a larger furnace, the technology we have developed to produce nearly 1 m x 0.5 m windows can also be
scaled to produce 1 m x 1 m sapphire windows.

ACKNOWLEDGMENTS

This work was supported by research contract FA8650-12-C-5168 from the United States Air Force Research
Laboratory (AFRL) Electronics & Sensors Branch, Manufacturing & Industrial Technologies Division, Materials &
Manufacturing Directorate.

REFERENCES
[1] Levine, J. B., Burks, T., Ciraldo, J., Montgomery, M., Novoselov, A., et al. “Synthesis and characterization of large
optical grade sapphire windows produced from a horizontal growth process,” Proc. SPIE 8708, 87080C (2013).
[2] Khattak, C. P., Filgate, J., Shetty, R., Schwerdtfeger, C. R., Ullal, S., “20-inch diameter CHES sapphire boules,”
Proc. SPIE 9453, 945305 (2015).
[3] “CLASS Sapphire Sheets,” Saint-Gobain Crystals,
https://web.archive.org/web/20170202150150/http://www.crystals.saint-gobain.com/products/sapphire-large-sheets-
class (2 February 2017).
[4] Locher, J., Jones, C., Bates, H., Rioux, J., “Characteristics of Thick (>12 mm) Class225 EFG Sapphire Sheet for IR
Window Applications,” Proc. SPIE 7302, 730203 (2009).
[5] Dobrovinskaya, E., Lytvynov L., Pischick, V. [Sapphire in science and engineering], STC “Institute for Single
Crystals,” National Academy of Sciences, Ukraine, 224-232 (2007).
[6] Puzikov, V. M., Dan’ko, A. Ya., Adonkin, G. T., Sidel’nikova, N. S., Tkachenko, V. F., Budnikov, A. T., “Optical
properties and fine faulty structure of sapphire crystals grown in low pressure CO gas atmosphere,” Semiconductor
Physics, Quantum Electronics & Optoelectronics, Vol. 3., No. 2, 185-190 (2000).
[7] Dan’ko, A. Ya., Nizhankovsky, S. V., Kanischev, V. N., Sidelnikova, N. S., Adonkin, G. T., Puzikov, V. M., Grin’,
L. A., “Growing of sapphire for optics and optoelectronics by the HDC method in a protective atmosphere,”
Functional Materials, 426-431 (2006).
[8] Bruni, F., Liu, C.-M., Stone-Sundberg, J., “Will Czochralski Growth of Sapphire Once Again Prevail?” Acta
Physica Polonica A, 213-218 (2013).

View publication stats